Colored curable composition, color filter and method of producing the same, and dipyrromethene metal complex compound and tautomer thereof

ABSTRACT

A colored curable composition is provided which has good developability, has excellent color purity, can be formed into a thin film, and has a high absorption coefficient. The colored curable composition includes at least one of specific dipyrromethene metal complex compounds and tautomers thereof. Also, a colored curable composition suitable for forming a color filter which is used in a liquid crystal display device or a solid-state imaging device, and a color filter using the colored curable composition and a method of producing the same are provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. Ser. No. 12/550,427, filed Aug.31, 2009, which claims priority under 35 USC 119 from Japanese PatentApplication Nos. 2008-225108 filed on Sep. 2, 2008 and 2008-251337 filedon Sep. 29, 2008, the disclosures of which are incorporated by referenceherein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a dipyrromethene metal complex compoundand a tautomer thereof, a colored curable composition suitable forforming a color filter which is used in a liquid crystal display deviceor a solid-state imaging device, and a color filter using the coloredcurable composition and a method of producing the same.

2. Description of the Related Art

One method of producing a color filter used in a liquid crystal displaydevice or a solid-state imaging device is a pigment dispersion method.There is a method of producing a color filter by photolithography usinga colored radiation-sensitive composition obtained by dispersing apigment in a variety of photosensitive compositions by the pigmentdispersion method. Since a pigment is used in this method, the resultantcomposition is stable with respect to light and heat, and sincepatterning is performed by photolithography, sufficient positionalprecision can be ensured. Thus, this method has been widely utilized asa method suitable for producing a color filter for a large screen and ahigh-definition color display.

In preparing a color filter by the pigment dispersion method, theradiation-sensitive composition is first applied onto a substrate with aspin coater or roll coater and dried to form a coating film. Then,colored pixels are obtained by pattern exposure and development of thecoating film. The color filter can be prepared by repeating thisoperation a number of times corresponding to the number of hues.

Recently, even higher resolution has become desirable in color filtersfor solid-state imaging devices; however, it is difficult to furtherimprove the resolution with conventional pigment dispersions. Problemssuch as the generation of color irregularities due to coarse particlesof the pigment result in a lack of suitability for uses which requirefine patterns such as solid state image sensing devices.

Use of a dye as the colorant has been conventionally studied from theviewpoint of improvement in resolution above (see, for example, JapanesePatent Application Laid-Open (JP-A) No. 6-75375). However, suchdye-containing curing compositions have the following additionalproblems:

(1) Dyes generally have lower light stability and/or lower heatresistance than pigments.

(2) It is difficult to obtain a liquid curable composition having adesired spectrum with a common colorant, because such a colorant is lesssoluble in an aqueous alkaline solution or organic solvent (hereinafter,also simply referred to as a “solvent”).

(3) It is difficult to control the solubility (developing efficiency) ofthe cured area and the uncured area, because the dye used ofteninteracts with other components in the curable composition.

(4) When the molar absorption coefficient (ε) of the dye used is low, alarge amount of the dye should be added, and thus the amounts of theother components in the curable composition, such as polymerizablecompound (monomer), binder, and photopolymerization initiator must bereduced, which leads to deterioration in the curing efficiency of thecomposition, the heat resistance after curing, and the developingefficiency of the cured area or uncured area.

Due to these problems, it has been difficult to form a thin film of finecolored patterns for high-definition color filters. Unlike those used inthe production of semiconductors, it is necessary to use a thin filmhaving a thickness of 1 μm or less for the production of color filtersfor solid-state imaging devices. It is thus necessary to add a largeramount of a colorant to the curable composition in order to obtain adesired absorption, leading to the problems described above.

Next, the conventional art with respect to a high fastness dye will bedescribed. Generally, coloring agents which are used in a variety ofapplications are commonly required to have the following properties.That is, the coloring agents are required to have absorption propertieswhich are preferable in terms of color reproducibility, fastness in useenvironment conditions (for example, good heat resistance, good lightresistance and good humidity resistance), and large molar absorptioncoefficients, and are required to be easily formed into a thin film.

For example, a dipyrromethene metal complex is known to be used as afunctional compound in a variety of applications, and is used as asensitizer for a radical polymerization initiator in a visiblephotopolymerization composition (see, for example, Japanese Patent Nos.3279035 and 3324279, and JP-A Nos. 11-352685, 11-352686, 2000-19729,2000-19738, and 2002-236360). In addition, the dipyrromethene metalcomplex is known to have a high molar absorption coefficient, and haveabsorption properties which are preferable in terms of colorreproducibility (see, for example, US Patent Application Publication No.2008/0076044 A1).

On the other hand, particularly in a color filter of a solid-stateimaging device, fine pattern forming properties are required, and it isdifficult to regulate solubility (developability) of a cured area and auncured area. Specifically, a fine pattern is formed by light exposurethrough a mask having a fine pattern, and subsequent development with analkaline liquid to dissolve an unexposed area in an alkali developer.However, when the solubility of a colored curable composition in analkali developer is poor, pattern forming properties are deteriorated(i.e., a colored material remains at an unexposed area). Accordingly, acolored curable composition having low dependency on the concentrationof the alkali liquid is sought.

SUMMARY OF THE INVENTION

According to a first aspect of the present invention, a colored curablecomposition is provided which has good developability, has excellentcolor purity, can be formed into a thin film, and has a high absorptioncoefficient.

Further, a color filter which is thin, has excellent color concentrationand color purity, and has excellent fastness, and a method of producingthe same are provided.

Still further, a dipyrromethene metal complex compound which has highsolvent solubility and fastness, has excellent absorption property, andhas a high molar absorption coefficient, and a tautomer thereof, arealso provided.

According to a second aspect of the invention, a magenta to violetcolored curable composition (i.e., a curable composition having any onecolor from magenta to violet) is provided which is useful for aprimary-colored color filter having blue, green and red colors, hasexcellent color purity, can be formed into a thin film, has a highabsorption coefficient, and has excellent pattern forming property.

Further, a magenta to violet color filter (i.e., a color filter havingany one color from magenta to violet) using the colored curablecomposition, which has excellent color purity, can be formed into a thinfilm, and has excellent fastness, and a method producing the same areprovided.

Still further, a colorant (i.e., a dipyrromethene metal complex) whichis useful in the colored curable composition useful for a color filter,has excellent absorption property, has a high molar absorptioncoefficient, and may impart favorable developability is also provided.

As the result of detailed study of various colorants, the inventors ofthe present invention have found that a dipyrromethene metal complexcompound having a specified substituent has a good hue, a highabsorption coefficient, excellent fastness, excellent solubility in anorganic solvent and excellent pattern forming properties (i.e., lowdependency on the concentration of an alkali developer), and completedthe invention based on these findings.

Aspects of the invention will be described below.

<1> A colored curable composition, including at least one selected fromthe group consisting of a compound represented by the following Formula(A1) and a tautomer thereof and a compound represented by the followingFormula (B1) and a tautomer thereof:

wherein, in Formula (A1) or Formula (B1), Ra represents a substituent; mrepresents an integer of 0, 1, 2, or 3; when there is more than one Ra,each Ra may be the same as or different from another Ra; M represents ahydrogen atom or an organic base or metal atom necessary forneutralizing a charge; L represents a single bond, an alkylene group,—O—, —N(Rb)—, —S—, —SO—, or —SO₂—, where Rb represents a hydrogen atom,an alkyl group, an aryl group, a heterocyclic group, an acyl group, acarbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group, or anarylsulfonyl group; R₁ to R₆ each independently represent a hydrogenatom or a substituent; R₇ represents a hydrogen atom, a halogen atom, analkyl group, an aryl group, or a heterocyclic group; at least one of R₁to R₆ represents a substituent and any one of the substituentsrepresented by R₁ to R₆ is a divalent linking group that binds to -L-;Ma represents a metal or a metal compound which may form a complex; X₁represents a group necessary for neutralizing a charge of Ma; X₂represents a group which may bind to Ma; p represents 0 or 1; and X₁ andX₂ may bind together to form a 5-membered, 6-membered or 7-memberedring.

<2> The colored curable composition according to <1>, wherein thecompound represented by Formula (A1) is a compound represented by thefollowing Formula (1-A1), and the compound represented by Formula (B1)is a compound represented by the following Formula (1-B1):

wherein, in Formula (1-A1) or Formula (1-B1), Ra represents asubstituent; m represents an integer of 0, 1, 2 or 3; when there is morethan one Ra, each Ra may be the same as or different from another Ra; Mrepresents a hydrogen atom, or an organic base or metal atom necessaryfor neutralizing a charge; L represents a single bond, an alkylenegroup, —O—, —N(Rb)—, —S—, —SO—, or —SO₂—, where Rb represents a hydrogenatom, an alkyl group, an aryl group, a heterocyclic group, an acylgroup, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonylgroup, or an arylsulfonyl group; R₂ to R₅ each independently represent ahydrogen atom or a substituent; R₇ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group, or a heterocyclic group; R₈ and R₉each independently represent an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an alkoxy group, an aryloxy group, an aminogroup, an anilino group, or a heterocyclic amino group; at least one ofR₂ to R₅, R₈ and R₉ represents a substituent and any one of thesubstituents represented by R₂ to R₅, R₈ and R₉ is a divalent linkinggroup that binds to -L-; Ma represents a metal or a metal compound; X₁represents a group necessary for neutralizing a charge of Ma; X₃ and X₄each independently represent NR, a nitrogen atom, an oxygen atom, or asulfur atom, where R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; Y₁ and Y₂ eachindependently represent NR or an oxygen atom, and R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group; R₈ and Y₁ may bind together to form a 5-membered,6-membered or 7-membered ring; and R₉ and Y₂ may bind together to form a5-membered, 6-membered, or 7-membered ring.

<3> The colored curable composition according to <1>, wherein thecompound represented by Formula (A-1) is a compound represented by thefollowing Formula (2-A1), and the compound represented by Formula (B-1)is a compound represented by the following Formula (2-B1):

wherein, Ra represents a substituent; m represents an integer of 0, 1, 2or 3; when there is more than one Ra, each Ra may be the same as ordifferent from another Ra; M represents a hydrogen atom, or an organicbase or metal atom necessary for neutralizing a charge; L represents asingle bond, an alkylene group, —O—, —N(Rb)—, —S—, —SO—, or —SO₂—, whereRb represents a hydrogen atom, an alkyl group, an aryl group, aheterocyclic group, an acyl group, a carbamoyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, or an arylsulfonyl group; R₂ to R₅ eachindependently represent a hydrogen atom or a substituent; R₇ representsa hydrogen atom, a halogen atom, an alkyl group, an aryl group, or aheterocyclic group; R₈ and R₉ each independently represent an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an alkoxygroup, an aryloxy group, an amino group, an anilino group, or aheterocyclic amino group; at least one of R₂ to R₅, R₈ and R₉ representsa substituent and any one of the substituents represented by R₂ to R₅,R₈ and R₉ is a divalent linking group that binds to -L-; Ma represents ametal or a metal compound; X₁ represents a group necessary forneutralizing a charge of Ma; X₃ and X₄ each independently represent NR,a nitrogen atom, an oxygen atom, or a sulfur atom, where R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group; Y₁ and Y₂ each independently represent NR or anoxygen atom, where R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; R₈ and Y₁ may bindtogether to form a 5-membered, 6-membered or 7-membered ring; and R₉ andY₂ may bind together to form a 5-membered, 6-membered, or 7-memberedring.

<4> The colored curable composition according to <1>, wherein Ma shownin Formula (A1) or Formula (B1) represents Fe, Zn, Co, V═O, or Cu.

<5> The colored curable composition according to <2>, wherein Ma shownin Formula (1-A1) or Formula (1-B1) represents Fe, Zn, Co, V═O, or Cu.

<6> The colored curable composition according to <3>, wherein Ma shownin Formula (2-A1) or Formula (2-B1) represents Fe, Zn, Co, V═O, or Cu.

<7> The colored curable composition according to <4>, wherein Marepresents Zn.

<8> A color filter, including the colored curable composition accordingto <1>.

<9> A method of producing a color filter, including:

applying the colored curable composition according to <1> onto a supportto form a coated film; and

exposing the coated film to light and developing the exposed coatedfilm, to form a pattern image.

<10> A compound represented by the following Formula (2-A1) or (2-B1),or a tautomer thereof:

wherein, in Formula (2-A1) or Formula (2-B1), Ra represents asubstituent; m represents an integer of 0, 1, 2 or 3; when there is morethan one Ra, each Ra may be the same as or different from another Ra; Mrepresents a hydrogen atom, or an organic base or metal atom necessaryfor neutralizing a charge; L represents a single bond, an alkylenegroup, —O—, —N(Rb)—, —S—, —SO—, or —SO₂—, where Rb represents a hydrogenatom, an alkyl group, an aryl group, a heterocyclic group, an acylgroup, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonylgroup, or an arylsulfonyl group; R₂ to R₅ each independently represent ahydrogen atom or a substituent; R₇ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group, or a heterocyclic group; R₈ and R₉each independently represent an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an alkoxy group, an aryloxy group, an aminogroup, an anilino group, or a heterocyclic amino group; at least one ofR₂ to R₅, R₈ and R₉ represents a substituent and any one of thesubstituents represented by R₂ to R₅, R₈ and R₉ is a divalent linkinggroup that binds to -L-; Ma represents a metal or a metal compound; X₁represents a group necessary for neutralizing a charge of Ma; X₃ and X₄each independently represent NR, a nitrogen atom, an oxygen atom, or asulfur atom, where R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; Y₁ and Y₂ eachindependently represent NR or an oxygen atom, where R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group; R₈ and Y₁ may bind together to form a 5-membered,6-membered or 7-membered ring; and R₉ and Y₂ may bind together to form a5-membered, 6-membered, or 7-membered ring.

<11> A compound represented by the following Formula (C1) or (D1), or atautomer thereof:

wherein, in Formula (C1) or Formula (D1), Ra represents a substituent; mrepresents an integer of 0, 1, 2 or 3; when there is more than one Ra,each Ra may be the same as or different from another Ra; n represents 0or 2; M represents a hydrogen atom, or an organic base or metal atomnecessary for neutralizing a charge; R₂ to R₅ each independentlyrepresent a hydrogen atom or a substituent; R₇ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group, or a heterocyclicgroup; R₁₀ and R₁₁ each independently represent an alkyl group, analkenyl group, an aryl group, or a heterocyclic group; at least one ofR₂ to R₅, R₁₀ and R₁₁ represents a substituent and any one of thesubstituents represented by R₂ to R₅, R₁₀ and R₁₁ is a divalent linkinggroup that binds to —S(═O)n-; and X₁ represents a group that can bind toZn.

<12> A colored curable composition, including at least one selected fromthe group consisting of a compound represented by the following Formula(A2) and a tautomer thereof and a compound represented by the followingFormula (B2) and a tautomer thereof:

wherein, in Formula (A2) or Formula (B2), R₁ to R₆ each independentlyrepresent a hydrogen atom or a substituent; R₇ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group, or a heterocyclicgroup; at least one of R₁ to R₆ represents a substituent and any one ofthe substituents represented by R₁ to R₆ is a divalent linking groupthat binds to -(L)-SO₃ ⁻ or -(L)-SO₃M; M represents a hydrogen atom, oran organic base or metal atom necessary for neutralizing a charge; Lrepresents an alkylene group, an aralkylene group, or an arylene group,or a divalent group which may be formed by a combination of divalentgroups selected from the group consisting of an alkylene group, anaralkylene group, an arylene group, —O—, —S—, —SO₂—, —N(Ra)—, —COO—,—OCO—, —CON(Rb)—, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—, —N(Rb)CON(Rc)—,—SO₂N(Rb)—, and —N(Rb)SO₂—, where Ra represents an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group and Rb and Rc eachindependently represent a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group; Ma represents a metal ora metal compound which may form a complex; X₁ represents a groupnecessary for neutralizing a charge of Ma; X₂ represents a group whichmay bind to Ma; p represents 0 or 1; and, in Formula (B2), X₁ and X₂ maybind together to form a 5-membered, 6-membered, or 7-membered ring.

<13> The colored curable composition according to <12>, wherein thecompound represented by Formula (A2) is a compound represented by thefollowing Formula (1-A2), and the compound represented by Formula (B2)is a compound represented by the following Formula (1-B2):

wherein, in Formula (1-A2) or Formula (1-B2), R₂ to R₅ eachindependently represent a hydrogen atom or a substituent; R₇ representsa hydrogen atom, a halogen atom, an alkyl group, an aryl group, or aheterocyclic group; R₈ and R₉ each independently represent an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an alkoxygroup, an aryloxy group, an amino group, an anilino group or aheterocyclic amino group; at least one of R₂ to R₅, R₈ and R₉ representsa substituent and any one of the substituents represented by R₂ to R₅,R₈ and R₉ is a divalent linking group to bind to -(L)-SO₃ ⁻ or-(L)-SO₃M; M represents a hydrogen atom, or an organic base or metalatom necessary for neutralizing a charge; L represents an alkylenegroup, an aralkylene group, or an arylene group, or a divalent groupwhich may be formed by a combination of divalent groups selected fromthe group consisting of an alkylene group, an aralkylene group, anarylene group, —O—, —S—, —SO₂—, —N(Ra)—, —COO—, —OCO—, —CON(Rb)—,—N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—, —N(Rb)CON(Rc)—, —SO₂N(Rb)—, and—N(Rb)SO₂—, where Ra represents an alkyl group, an alkenyl group, anaryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group,or an arylsulfonyl group and Rb and Rc each independently represent ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, or aheterocyclic group; Ma represents a metal or metal compound which mayform a complex; X₁ represents a group necessary for neutralizing acharge of Ma; X₃ and X₄ each independently represent NR, an oxygen atom,or a sulfur atom, where R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; R and R₈ or R₉ may bindtogether to form a 5-membered, 6-membered, or 7-membered ring; Y₁ and Y₂each independently represent NR or an oxygen atom, where R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group; R₈ and Y₁ may bind together to form a 5-membered,6-membered, or 7-membered ring; and R₉ and Y₂ may bind together to forma 5-membered, 6-membered, or 7-membered ring.

<14> The colored curable composition according to <12>, wherein Marepresents Fe, Zn, Co, V═O, or Cu.

<15> The colored curable composition according to <12>, wherein Marepresents Zn.

<16> A colored curable composition, including at least one selected fromthe group consisting of a compound represented by the following Formula(C2) and a tautomer thereof and a compound represented by the followingFormula (D2) and a tautomer thereof:

wherein, in Formula (C2) or Formula (D2), R₂ to R₅ each independentlyrepresent a hydrogen atom or a substituent; R₇ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group, or a heterocyclicgroup; R₁₀ and R₁₁ each independently represent an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an alkoxy group, anaryloxy group, an amino group, an anilino group, or a heterocyclic aminogroup; at least one of R₂ to R₅, R₁₀ and R₁₁ represents a substituentand any one of the substituents represented by R₂ to R₅, R₁₀ and R₁₁ isa divalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M; Mrepresents a hydrogen atom, or an organic base or metal atom necessaryfor neutralizing a charge; L represents an alkylene group, an aralkylenegroup, or an arylene group, or a divalent group which may be formed by acombination of divalent groups selected from the group consisting of analkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO₂—,—N(Ra)—, —COO—, —OCO—, —CON(Rb)—, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—,—N(Rb)CON(Rc)—, —SO₂N(Rb)—, and —N(Rb)SO₂—, where Ra represents an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group, or an arylsulfonyl group and Rb and Rceach independently represent a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group; and X₁ represents a groupnecessary for neutralizing a charge of Zn.

<17> A color filter including the colored curable composition accordingto <12>.

<18> A method of producing a color filter, including:

applying the colored curable composition according to <12> onto asupport to form a coated film;

exposing the coated film to light through a mask, and developing thecoated film to form a pattern image.

<19> A colorant, selected from the group consisting of a compoundrepresented by Formula (C2) and a tautomer thereof and a compoundrepresented by Formula (D2) and a tautomer thereof:

wherein, in Formula (C2) or Formula (D2), R₂ to R₅ each independentlyrepresent a hydrogen atom or a substituent; R₇ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group, or a heterocyclicgroup; R₁₀ and R₁₁ each independently represent an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an alkoxy group, anaryloxy group, an amino group, an anilino group, or a heterocyclic aminogroup; at least one of R₂ to R₅, R₁₀ and R₁₁ represents a substituentand any one of the substituents represented by R₂ to R₅, R₁₀ and R₁₁ isa divalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M; Mrepresents a hydrogen atom, or an organic base or metal atom necessaryfor neutralizing a charge; L represents an alkylene group, an aralkylenegroup, or an arylene group, or a divalent group which may be formed by acombination of divalent groups selected from the group consisting of analkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO₂—,—N(Ra)—, —COO—, —OCO—, —CON(Rb)—, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—,—N(Rb)CON(Rc)—, —SO₂N(Rb)—, and —N(Rb)SO₂—, where Ra represents an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group, or an arylsulfonyl group and Rb and Rceach independently represent a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group; and X₁ represents a groupnecessary for neutralizing a charge of Zn.

According to the first aspect of the present invention, a coloredcurable composition is provided which has good developability, hasexcellent color purity, can be formed into a thin film, and has a highabsorption coefficient.

Further, according to the first aspect of the invention, a color filterwhich is thin, has excellent color concentration and color purity, and,has excellent fastness, and a method of producing the same are provided.

Still further, according to the first aspect of the invention, adipyrromethene metal complex compound which has high solvent solubilityand fastness, has excellent absorption property, and has a high molarabsorption coefficient, and a tautomer thereof are also provided.

According to the second aspect of the invention, a colored curablecomposition including a dipyrromethene metal complex having a specifiedsubstituent is provided, which is useful in a primary-colored colorfilter having blue, green and red colors, has excellent color purity,can be formed in to a thin film, has a high absorption coefficient, hasexcellent fastness, has low solubility in an organic solvent, anddependency on a concentration of an alkali developer, and excellent inpattern forming property.

Further, according to the second aspect of the invention, a color filterwhich has excellent color purity, can be formed into a thin film, hasexcellent fastness, and has high resolution, and a method of producingthe same are provided.

Still further, according to the second aspect of the invention, acolorant (i.e., a dipyrromethene metal complex) which is useful in acolored curable composition useful for a color filter, has excellentabsorption property, has a high molar absorption coefficient, and mayimpart suitable developability is provided.

DETAILED DESCRIPTION OF THE INVENTION

Hereinbelow, the colored curable composition, the color filter, and theprocess for producing the color filter of the present invention will bedescribed in detail.

Colored Curable Composition

Colored Curable Composition of First Exemplary Embodiment

The colored curable composition according to a first exemplaryembodiment of the invention includes, as a coloring agent, at least oneselected from a dipyrromethene metal complex compound having a specifiedsubstituent represented by the following Formula (A1) and adipyrromethene metal complex compound having a specified substituentrepresented by the following Formula (B1), and tautomers thereof.

It is preferable that the colored curable composition according to thefirst exemplary embodiment of the invention is an ultraviolet-sensitivecolored curable composition.

Compounds Represented by Formula (A1) and Formula (B1), and TautomersThereof

In Formula (A1) and Formula (B1), Ra represents a substituent, mrepresents an integer of 0, 1, 2, or 3, and M represents a hydrogen atomor an organic base or metal atom necessary for neutralizing a charge.

L represents a single bond, an alkylene group, —O—, —N(Rb)—, —S—, —SO—,or —SO₂—, and Rb represents a hydrogen atom, an alkyl group, an arylgroup, a heterocyclic group, an acyl group, a carbamoyl group, analkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.

R₁ to R₆ each independently represent a hydrogen atom or a substituent,and R₇ represents a hydrogen atom, a halogen atom, an alkyl group, anaryl group, or a heterocyclic group, provided that any one of thesubstituents represented by R₁ to R₆ is a divalent linking group thatbinds to -L-.

Ma represents a metal or a metal compound which may form a complex.

X₁ represents a group necessary for neutralizing a charge of Ma; X₂represents a group which may bind to Ma; p represents 0 or 1; and X₁ andX₂ may bind together to form a 5-membered, 6-membered or 7-memberedring.

Formula (A1) and Formula (B1) will be described in detail.

Ra in Formula (A1) or Formula (B1) represents a substituent. Examples ofthe substituent represented by Ra include a halogen atom (for example,fluorine, chlorine, bromine), an alkyl group (for example, a straight,branched or cyclic alkyl group having preferably 1 to 48 carbon atoms,more preferably 1 to 24 carbon atoms; examples thereof include a methylgroup, an ethyl group, a propyl group, an isopropyl group, a butylgroup, a t-butyl group, a pentyl group, a hexyl group, a heptyl group,an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecylgroup, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a1-norbornyl group, and a 1-adamantyl group), an alkenyl group (forexample, an alkenyl group having preferably 2 to 48 carbon atoms, morepreferably 2 to 18 carbon atoms; examples thereof include a vinyl group,an allyl group, and a 3-buten-1-yl group), an aryl group (for example,an aryl group having preferably 6 to 48 carbon atoms, more preferably 6to 24 carbon atoms; examples thereof include a phenyl group and anaphthyl group), a heterocyclic group (for example, a heterocyclic grouphaving preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbonatoms; examples thereof include a 2-thienyl group, a 4-pyridyl group, a2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and abenzotriazol-1-yl group), a silyl group (for example, a silyl grouphaving preferably 3 to 38 carbon atoms, more preferably 3 to 18 carbonatoms; examples thereof include a trimethylsilyl group, a triethylsilylgroup, a tributylsilyl group, a t-butyldimethylsilyl group, and at-hexyldimethylsilyl group), a hydroxyl group, a cyano group, a nitrogroup, an alkoxy group (for example, an alkoxy group having preferably 1to 48 carbon atoms, more preferably 1 to 24 carbon atoms; examplesthereof include a methoxy group, an ethoxy group, a 1-butoxy group, a2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxygroup, and a cycloalkyloxy group such as a cyclopentyloxy group or acyclohexyloxy group), an aryloxy group (for example, an aryloxy grouphaving preferably 6 to 48 carbon atoms, more preferably 6 to 24 carbonatoms; examples thereof include a phenoxy group and a 1-naphthoxygroup), a heterocyclic oxy group (for example, a heterocyclic oxy grouphaving preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbonatoms; examples thereof include a 1-phenyltetrazol-5-oxy group and a2-tetrahydropyranyloxy group), a silyloxy group (for example, a silyloxygroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms; examples thereof include a trimethylsilyloxy group, at-butyldimethylsiliyloxy group, and a diphenylmethylsilyloxy group), anacyloxy group (for example, an acyloxy group having preferably 2 to 48carbon atoms, more preferably 2 to 24 carbon atoms; examples thereofinclude an acetoxy group, a pivaloyloxy group, a benzoyloxy group, and adodecanoyloxy group), an alkoxycarbonyloxy group (for example, analkoxycarbonyloxy group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms; examples thereof include anethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and acycloalkyloxycarbonyloxy group such as a cyclohexyloxycarbonyloxygroup), an aryloxycarbonyloxy group (for example, an aryloxycarbonyloxygroup having preferably 7 to 32 carbon atoms, more preferably 7 to 24carbon atoms; examples thereof include a phenoxycarbonyloxy group), acarbamoyloxy group (for example, a carbamoyloxy group having preferably1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms; examplesthereof include a N,N-dimethylcarbamoyloxy group, a N-butylcarbamoyloxygroup, N-phenylcarbamoyloxy group, and a N-ethyl-N-phenylcarbamoyloxygroup), a sulfamoyloxy group (for example, a sulfamoyloxy group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms;examples thereof include a N,N-diethylsulfamoyloxy group and aN-propylsulfamoyloxy group), an alkylsulfonyloxy group (for example, analkylsulfonyloxy group having preferably 1 to 38 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include amethylsulfonyloxy group, a hexadecylsulfonyloxy group, and acyclohexylsulfonyloxy group),

an arylsulfonyloxy group (for example, an arylsulfonyloxy group havingpreferably 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms;examples thereof include a phenylsulfonyloxy group), an acyl group (forexample, an acyl group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include a formylgroup, an acetyl group, a pivaloyl group, a benzoyl group, atetradecanoyl group, and a cyclohexanoyl group), an alkoxycarbonyl group(for example, an alkoxycarbonyl group having preferably 2 to 48 carbonatoms, more preferably 2 to 24 carbon atoms; examples thereof include amethoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonylgroup, a cyclohexyloxycarbonyl group, and a2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), anaryloxycarbonyl group (for example, an aryloxycarbonyl group havingpreferably 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms;examples thereof include a phenoxycarbonyl group), a carbamoyl group(for example, a carbamoyl group having preferably 1 to 48 carbon atoms,more preferably 1 to 24 carbon atoms; examples thereof include acarbamoyl group, a N,N-diethylcarbamoyl group, aN-ethyl-N-octylcarbamoyl group, a N,N-dibutylcarbamoyl group, aN-propylcarbamoyl group, a N-phenylcarbamoyl group, aN-methyl-N-phenylcarbamoyl group, and a N,N-dicyclohexylcarbamoylgroup), an amino group (for example, an amino group having preferably 32or less carbon atoms, more preferably 24 or less carbon atoms; examplesthereof include an amino group, a methylamino group, a N,N-dibutylaminogroup, a tetradecylamino group, a 2-ethylhexylamino group, and acyclohexylamino group), an anilino group (for example, an anilino grouphaving preferably 6 to 32 carbon atoms, more preferably 6 to 24 carbonatoms; examples thereof include an anilino group and a N-methylanilinogroup), a heterocyclic amino group (for example, a heterocyclic aminogroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms; examples thereof include a 4-pyridyl amino group), acarbonamido group (for example, a carbonamido group having preferably 2to 48 carbon atoms, more preferably 2 to 24 carbon atoms; examplesthereof include an acetamide group, a benzamide group, atetradecaneamido group, a pivaloylamido group, and a cyclohexaneamidogroup), a ureido group (for example, a ureido group having preferably 1to 32 carbon atoms, more preferably 1 to 24 carbon atoms; examplesthereof include a ureido group, a N,N-dimethylureido group, and aN-phenylureido group), an imido group (for example, an imido grouphaving preferably 36 or less carbon atoms, more preferably 24 or lesscarbon atoms; examples thereof include a N-succinimido group and aN-phthalimido group), an alkoxycarbonylamino group (for example, analkoxycarbonylamino group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms; examples thereof include amethoxycarbonylamino group, an ethoxycarbonylamino group, at-butoxycarbonylamino group, an octadecyloxycarbonylamino group, and acyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (forexample, an aryloxycarbonylamino group having preferably 7 to 32 carbonatoms, more preferably 7 to 24 carbon atoms; examples thereof include aphenoxycarbonylamino group), a sulfonamido group (for example, asulfonamido group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include amethanesulfonamido group, a butanesulfonamido group, abenzenesulfonamido group, a hexadecanesulfonamido group, and acyclohexanesulfonamido group), a sulfamoylamino group (for example, asulfamoylamino group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include aN,N-dipropylsulfamoylamino group and a N-ethyl-N-dodecylsulfamoylaminogroup), an azo group (for example, an azo group having preferably 1 to32 carbon atoms, more preferably 1 to 24 carbon atoms; examples thereofinclude a phenylazo group and a 3-pyrazolylazo group), an alkylthiogroup (for example, an alkylthio group having preferably 1 to 48 carbonatoms, more preferably 1 to 24 carbon atoms; examples thereof include amethylthio group, an ethylthio group, an octylthio group, and acyclohexylthio group), an arylthio group (for example, an arylthio grouphaving preferably 6 to 48 carbon atoms, more preferably 6 to 24 carbonatoms; examples thereof include a phenylthio group),

a heterocyclic thio group (for example, a heterocyclic thio group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms;examples thereof include a 2-benzothiazolylthio group, a 2-pyridylthiogroup, and a 1-phenyltetrazolylthio group), an alkylsulfinyl group (forexample, an alkylsulfinyl group having preferably 1 to 32 carbon atoms,more preferably 1 to 24 carbon atoms; examples thereof include adodecanesulfinyl group), an arylsulfinyl group (for example, anarylsulfinyl group having preferably 6 to 32 carbon atoms, morepreferably 6 to 24 carbon atoms; examples thereof include aphenylsulfinyl group), an alkylsulfonyl group (for example, analkylsulfonyl group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include amethylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, abutylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonylgroup, a hexadecylsulfonyl group, an octylsulfonyl group, and acyclohexylsulfonyl group), an arylsulfonyl group (for example, anarylsulfonyl group having preferably 6 to 48 carbon atoms, morepreferably 6 to 24 carbon atoms; examples thereof include aphenylsulfonyl group and a 1-naphthylsulfonyl group), a sulfamoyl group(for example, a sulfamoyl group having preferably 32 or less carbonatoms, more preferably 24 or less carbon atoms; examples thereof includea sulfamoyl group, a N,N-dipropylsulfamoyl group, aN-ethyl-N-dodecylsulfamoyl group, a N-ethyl-N-phenylsulfamoyl group, anda N-cyclohexylsulfamoyl group), a sulfo group, a phosphonyl group (forexample, a phosphonyl group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include aphenoxyphosphonyl group, an octyloxyphosphonyl group, and aphenylphosphonyl group), a phosphinoylamino group (for example, aphosphinoylamino group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include adiethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group).

When plural Ra's are included in Formula (A1) or (B1) or the tautomersthereof, the plural Ra's may be the same as or different from eachother.

When the substituent represented by Ra in Formula (A1) or Formula (B1)may further have at least one additional substituent, the additionalsubstituent may be any one of the substituents represented by Ra. Whenthe substituent represented by Ra is substituted with 2 or moreadditional substituents, the additional substituents may be the same asor different from each other.

In Formula (A1) or Formula (B1), m represents 0, 1, 2, or 3, preferablyrepresents 0 or 1, and more preferably represents 0.

M in Formula (A1) or Formula (B1) represents a hydrogen atom, or anorganic base or metal atom necessary for neutralizing a charge. Examplesof the organic base include alkylamines, anilines, quaternary amines,guanidines, pyridines, and quinolines. Examples of the metal atominclude alkali metal atoms. As M in Formula (A1) and Formula (B1),ammonia is also preferable. M is most preferably a hydrogen atom.

L in Formula (A1) or Formula (B1) represents a single bond, an alkylenegroup, —O—, —N(Rb)—, —S—, —SO—, or —SO₂—, and Rb represents a hydrogenatom, an alkyl group, an aryl group, a heterocyclic group, an acylgroup, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonylgroup, or an arylsulfonyl group.

The alkyl group, the aryl group, the heterocyclic group, the acyl group,the carbamoyl group, the alkoxycarbonyl group, the alkylsulfonyl group,and the arylsulfonyl group represented by Rb may each be furthersubstituted with at least one additional substituent that is any one ofthe substituents represented by Ra. When one of these groups issubstituted with 2 or more additional substituents, the additionalsubstituents may be the same as or different from each other.

L is preferably an alkylene group, —O—, —S—, or —SO₂—, most preferably—S—, or —SO₂—.

R₁ to R₆ in Formula (A1) or Formula (B1) each independently represent ahydrogen atom or a substituent, and any one of the substituentsrepresented by R₁ to R₆ is a divalent linking group that binds to -(L)-(a group which is the linking group in this case will be explained by acase where the -(L)- group is a hydrogen atom).

The substituents represented by R₁ to R₆ each have the same meanings asthe substituents represented by Ra of Formula (A1) or Formula (B1), andpreferable ranges and examples thereof are also the same.

When substituents represented by R₁ to R₆ may each further have at leastone additional substituent, the additional substituent may be any one ofthe substituents represented by Ra. When a substituent represented by R₁to R₆ is substituted with 2 or more additional substituents, theadditional substituents may be the same as or different from each other.

When any one of the substituents represented by R₁ to R₆ is a divalentlinking group, the divalent linking group may be a new divalent linkinggroup formed by binding at least two substituents. For example, the newdivalent linking group may be formed by binding at least two divalentlinking groups selected from the group consisting of an alkylene group,an aralkylene group, an arylene group, a divalent heterocyclic group,—O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rc)—, —C(═O)N(Rc)—,—N(Rc)C(═O)—, —N(Rc)C(═O)O—, —N(Rc)C(═O)N(Rd)—, —C(═O)N(Rc)C(═O)—, —SO—,—SO₂—, —SO₃—, —SO₂N(Rc)—, —N(Rc)SO₂—, —C(═O)N(Rc)SO₂—, and—SO₂N(Rc)SO₂—.

Rc and Rd each independently represent a hydrogen atom, an alkyl group,an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,or a sulfamoyl group. The alkyl group, aryl group, heterocyclic group,acyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonylgroup, carbamoyl group, and sulfamoyl group may each be substituted withan additional group which is any one of the substituents represented byRa, and when substituted with 2 or more additional substituents, theadditional substituents may be the same as or different from each other.

R₇ in Formula (A1) or Formula (B1) represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group, or a heterocyclic group.

The alkyl group, the aryl group, and the heterocyclic group representedby R₇ have the same meanings as the alkyl group, the aryl group, and theheterocyclic group represented by Ra of Formula (A1) or Formula (B1),and the preferable ranges and examples thereof are also the same.

The alkyl group, the aryl group, or the heterocyclic group representedby R₇ may be substituted with an additional substituent which is any oneof the substituents represented by Ra, and when they are substitutedwith 2 or more additional substituents, the additional substituents maybe the same as or different from each other.

R₇ is preferably a hydrogen atom, an alkyl group, or an aryl group, morepreferably a hydrogen atom.

Ma in Formula (A1) or Formula (B1) represents a metal or a metalcompound which may form a complex.

The metal and the metal compound represented by Ma may be a divalentmetal atom, a divalent metal oxide, a divalent metal hydroxide, or adivalent metal chloride. Example thereof include metals such as Zn, Mg,Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, or Fe metal chlorides suchas AlCl, InCl, FeCl, TiCl₂, SnCl₂, SiCl₂, or GeCl₂, metal oxides such asTiO or V═O, and metal hydroxides such as Si(OH)₂.

Among them, from the viewpoints of stability, spectroscopic property,heat resistance, light resistance, and production suitability of acomplex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or V═O ispreferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V═O is morepreferable, Fe, Zn, Co, V═O, or Cu is further preferable, and Zn is mostpreferable.

X₁ in Formula (B1) represents a group necessary for neutralizing acharge of Ma, and examples thereof include a halogen atom, a hydroxylgroup, a carboxylic acid group, a phosphoric acid group, and a sulfonicacid group.

X₂ in Formula (A1) or Formula (B1) may be any group as long as it is agroup which may bind to Ma, and examples thereof include water, alcohols(e.g. methanol, ethanol, propanol), and compounds described in “MetalChelate” [1] Takeichi Sakaguchi, Keihei Ueno (1995, Nankodo Co., Ltd.),[2] (1996), and [3] (1997).

In Formula (A1) or Formula (B1), p represents 0 or 1.

X₁ and X₂ in Formula (A1) or Formula (B1) may bind to each other to forma 5-membered, 6-membered, or 7-membered ring with Ma. The 5-membered,6-membered, or 7-membered ring may be a saturated or unsaturated ring.The 5-membered, 6-membered or 7-membered ring may contain only carbonatoms or may be a heterocyclic ring having at least one atom selectedfrom nitrogen, oxygen and sulfur atoms.

From the viewpoints of synthesis suitability, and stability and fastnessof a compound, the compound represented by Formula (A1) or Formula (B1),or the tautomer thereof is preferably a dipyrromethene metal complexrepresented by Formula (1-A1) or Formula (1-B1), or a tautomer thereof.

Compounds Represented by Formula (1-A1) and Formula (1-B1) and TautomersThereof

In the formulas, Ra represents a substituent; m represents an integer of0, 1, 2 or 3; and M represents a hydrogen atom, or an organic base ormetal atom necessary for neutralizing a charge. When there are pluralRa's, the plural Ra's may be the same as or different from each other. Lrepresents a single bond, an alkylene group, —O—, —N(Rb)—, —S—, —SO—, or—SO₂—, and Rb represents a hydrogen atom, an alkyl group, an aryl group,a heterocyclic group, an acyl group, a carbamoyl group, analkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.

R₂ to R₅ each independently represent a hydrogen atom or a substituent.R₇ represents a hydrogen atom, a halogen atom, an alkyl group, an arylgroup, or a heterocyclic group. R₈ and R₉ each independently representan alkyl group, an alkenyl group, an aryl group, a heterocyclic group,an alkoxy group, an aryloxy group, an amino group, an anilino group, ora heterocyclic amino group, provided that any one of the substituentsrepresented by R₂ to R₅, R₈ and R₉ is a divalent linking group thatbinds to -L-.

Ma represents a metal or a metal compound; X₁ represents a groupnecessary for neutralizing a charge of Ma; X₃ and X₄ each independentlyrepresent NR (in which R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, anoxygen atom, or a sulfur atom; Y₁ and Y₂ each independently represent NR(in which R represents a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group), or an oxygen atom; R₈and Y₁ may bind together to form a 5-membered, 6-membered or 7-memberedring; and R₉ and Y₂ may bind together to form a 5-membered, 6-membered,or 7-membered ring. X₁ represents a group necessary for neutralizing acharge of Ma.

Hereinbelow, Formula (1-A1) and Formula (1-B1) will be described indetail.

Ra, m, M, L, R₂ to R₅, R₇, Ma and X₁ shown in Formula (1-A1) or Formula(1-B1) have the same meanings as those shown in Formula (A1) or Formula(B1), and the preferable ranges and examples thereof are also the same.

Any one of the substituents represented by R₂ to R₅, R₈ and R₉ inFormula (1-A1) or Formula (1-B1) is a divalent linking group that bindsto -L-, and explanation of this any divalent group of R₂ to R₅, R₈ andR₉ is expressed by substituent of a hydrogen atom for -L-.

R₈ and R₉ in Formula (1-A1) or Formula (1-B1) each independentlyrepresent an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an alkoxy group, an aryloxy group, an amino group,an anilino group, or a heterocyclic amino group.

The preferable ranges and examples of the alkyl group, the alkenylgroup, the aryl group, the heterocyclic group, the alkoxy group, thearyloxy group, the amino group, the anilino group and the heterocyclicamino group represented by R₈ or R₉ are the same as those of thesubstituents represented by Ra.

The alkyl group, the alkenyl group, the aryl group, the heterocyclicgroup, the alkoxy group, the aryloxy group, the amino group, the anilinogroup and the heterocyclic amino group represented by R₈ or R₉ may eachbe further substituted with an additional substituent which is any oneof the substituents represented by Ra. When they are substituted withtwo or more additional substituents, the additional substituents may bethe same as or different from each other.

R₈ and R₉ are each preferably an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an alkoxy group, an amino group, or ananilino group, more preferably an alkyl group, an alkenyl group, or anaryl group, and most preferably an alkyl group or an aryl group.

When a substituent represented by R₈ or R₉ is a divalent linking group,the divalent linking group may be a new divalent linking group formed bybinding at least two substituents. For example, the new divalent linkinggroup may be formed by binding at least two divalent linking groupsselected from the group consisting of an alkylene group, an aralkylenegroup, an arylene group, a divalent heterocyclic group, —O—, —S—,—C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rc)—, —C(═O)N(Rc)—, —N(Rc)C(═O)—,—N(Rc)C(═O)O—, —N(Rc)C(═O)N(Rd)—, —SO—, —SO₂—, —SO₃—, —SO₂N(Rc)—,—N(Rc)SO₂—, —C(═O)N(Rc)SO₂—, and —SO₂N(Rc)SO₂—.

Rc and Rd each independently represent a hydrogen atom, an alkyl group,an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,or a sulfamoyl group. These alkyl group, aryl group, heterocyclic group,acyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonylgroup, carbamoyl group, and sulfamoyl group may be substituted with anadditional substituent which is any one of the substituents representedby Ra. When they are substituted with two or more additionalsubstituents, the additional substituents may be the same as ordifferent from each other.

X₃ and X₄ in Formula (1-A1) or Formula (1-B1) each independentlyrepresent NR (in which R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, anoxygen atom, or a sulfur atom. Preferable examples of the alkyl group,the alkenyl group, the aryl group, the heterocyclic group, the acylgroup, the alkylsulfonyl group, and the arylsulfonyl group representedby R are the same as the alkyl group, the alkenyl group, the aryl group,the heterocyclic group, the acyl group, the alkylsulfonyl group, and thearylsulfonyl group represented by Ra.

When R may further have at least one additional substituent, theadditional substituent may be any one of the substituents represented byRa. When R is substituted with two or more additional substituents, theadditional substituents may be the same as or different from each other.

X₃ and X₄ each represent preferably NR (in which R is a hydrogen atom,an alkyl group, an aryl group, an alkylsulfonyl group, or anarylsulfonyl group) or an oxygen atom, and from the viewpoints ofsynthesis suitability, and stability and fastness of a compound, anoxygen atom is most preferable.

Y₁ and Y₂ in Formula (1-A1) or Formula (1-B1) each independentlyrepresent NR (in which R is a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group) or an oxygen atom, and Rin NR has the same meaning as that of R in NR as an example of X₃ andX₄.

In Formula (1-A1) or Formula (1-B1), R₈ and Y₁ may bind together to forma 5-membered, 6-membered or 7-membered ring; and R₉ and Y₂ may bindtogether to form a 5-membered, 6-membered, or 7-membered ring. X₁represents a group necessary for neutralizing a charge.

Formula (A1) and Formula (1-A1) are respectively further preferablyrepresented by Formula (2-A1), and Formula (B1) and Formula (1-B1) arerespectively further preferably represented by Formulae (2-B1).

Compounds Represented by Formula (2-A1) and Formula (2-B1)

In the formulas, Ra, m, M, L, R₂ to R₅, R₇, R₈, R₉, Ma, X₁, X₃, X₄, Y₁,and Y₂ have the same meanings as in Formula (1-A1) and Formula (1-B1),respectively, and the preferable ranges and examples thereof are alsothe same.

Tautomers of the compounds represented by Formula (1-A1), Formula(1-B1), Formula (2-A1), and Formula (2-B1) will be described.

Tautomers of compounds represented by Formula (1-A1), Formula (1-B1),Formula (2-A1), and Formula (2-B1) may be any tautomer thereof as longas it is a compound having a structure which may be formed by movementof one hydrogen atom in the molecule of the compound. For example, thepyrromethene skeletons of Formula (1-A1), Formula (1-B1), Formula(2-A1), and Formula (2-B1) may each be one of the structures representedby the following Formula (a) to Formula (f).

Respective substituents in the formulas have the same meanings as inFormula (1-A1), Formula (1-B1), Formula (2-A1), and Formula (2-B1). X₁has the same meanings as that of X₁ of Formula (1-A1).

From the viewpoints of synthesis suitability, and stability andsolubility in an organic solvent of a compound, Formula (1-A1) andFormula (2-A1) are each further preferably represented by the followingFormula (C1) or a tautomer thereof, and Formula (1-B1) and Formula(2-B1) are each further preferably represented by the following Formula(D1) or a tautomer thereof.

Compounds Represented by Formula (C1) and Formula (D1)

In the formulas, Ra, m, M, R₂ to R₅, R₇ and X₁ have the same meanings asin Formula (A1), Formula (B1), Formula (1-A1), and Formula (1-B1), andthe preferable ranges and examples thereof are also the same.

In the formulas, n represents 0 or 2, and R₁₀ and R₁₁ each independentlyrepresent an alkyl group, an alkenyl group, an aryl group, or aheterocyclic group, provided that any one of the substituentsrepresented by R₂ to R₅, R₁₀, and R₁₁ is a divalent linking group thatbinds to —S(═O)n-.

R₁₀ and R₁₁ in Formula (C1) or Formula (D1) each independently representan alkyl group, an alkenyl group, an aryl group, or a heterocyclicgroup.

The alkyl group, the alkenyl group, the aryl group, and the heterocyclicgroup represented by R₁₀ or R₁₁ may each be further substituted with anadditional substituent that is any one of the substituents representedby Ra. When they are substituted with two or more additionalsubstituents, the additional substituents may be same as or differentfrom each other.

From the viewpoints of synthesis suitability, and stability of acompound, R₁₀ and R₁₁ each preferably independently represent an alkylgroup or an aryl group.

—S(═O)n- is preferably bound to any one of R₁₀ and R₁₁, from theviewpoint of synthesis suitability.

When a substituent represented by R₁₀ or R₁₁ is a divalent linkinggroup, the divalent linking group may be a new divalent linking groupformed by binding at least two substituents. For example, the newdivalent linking group may be formed by binding at least tow divalentlinking groups selected from the group consisting of an alkylene group,an aralkylene group, an arylene group, a divalent heterocyclic group,—O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rc)—, —C(═O)N(Rd)—,—N(Rc)C(═O)—, —N(Rc)C(═O)O—, —N(Rc)C(═O)N(Rd)—, —SO—, —SO₂—, —SO₃—,—SO₂N(Rc)—, —N(Rc)SO₂—, —C(═O)N(Rc)SO₂—, and —SO₂N(Rc)SO₂—.

Rc and Rd each independently represent a hydrogen atom, an alkyl group,an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,or a sulfamoyl group. These alkyl group, aryl group, heterocyclic group,acyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonylgroup, carbamoyl group, and sulfamoyl group may each be substituted withat least one additional substituent that is any one of the substituentsrepresented by Ra. When they are substituted with two or more additionalsubstituents, the additional substituents may be the same as ordifferent from each other.

Next, a preferable range of the compounds of the first exemplaryembodiment of the invention will be described.

Formula (A1) is more preferable than Formula (B1), Formula (1-A1) ismore preferable than Formula (1-B1), Formula (2-A1) is more preferablethan Formula (2-B1), and Formula (C1) is more preferable than Formula(D1).

Formula (A1) and Formula (B1) are respectively preferably represented bythe corresponding Formula (1-A1) and Formula (1-B1), more preferablyrepresented by the corresponding Formula (2-A1) and Formula (2-B1), andare further preferably represented by the corresponding Formula (C1) andFormula (D1).

In Formula (A1) and Formula (B1), it is preferable that any one of R₁ orR₆ is a divalent linking group that binds to -L-. In Formula (1-A1),Formula (1-B1), Formula (2-A1), and Formula (2-B1), it is preferablethat R₈ or R₉ is a divalent linking group that binds to -L-. Further, inFormula (C1) and Formula (D1), it is preferable that R₁₀ or R₁₁ is adivalent linking group that binds to —S(═O)n-.

When any one of R₁ to R₆ of Formula (A1) or Formula (B1) is a divalentlinking group that binds to -L-, the divalent linking group ispreferably an alkylene group, an aralkylene group, an arylene group, ora divalent heterocyclic group or a divalent linking group formed by anyone of an alkylene group, an aralkylene group, and an arylene group, andany one of —O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rc)—,—C(═O)N(Rd)—, —N(Rc)C(═O)—, —N(Rc)C(═O)O—, —N(Rc)C(═O)N(Rd)—, —SO—,—SO₂—, —SO₂N(Rc)—, and —N(Rc)SO₂—). Further preferable is an alkylenegroup, an aralkylene group, or an arylene group.

When any one of R₂ to R₅, R₈ and R₉ in Formula (1-A1), Formula (1-B1),Formula (2-A1), or Formula (2-B1) is a divalent linking group that bindsto -L-, it is preferable that -L-binds to R₈ or R₉. The divalent linkinggroup is preferably an alkylene group, an aralkylene group, an arylenegroup, or a divalent heterocyclic group, or a divalent linking groupformed by binding any one of an alkylene group, an aralkylene group, andan arylene group, and any one of —O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—,—OC(═O)N(Rc)—, —C(═O)N(Rd)-, —N(Rc)C(═O)—, —N(Rc)C(═O)O—,—N(Rc)C(═O)N(Rd)—, —SO—, —SO₂—, —SO₂N(Rc)-, and —N(Rc)SO₂—). Furtherpreferable is an alkylene group, an aralkylene group, or an arylenegroup.

When any one of R₂ to R₅, R₁₀, and R₁₁ in Formula (C1) or Formula (D1)is a divalent linking group that binds to —S(═O)n-, —S(═O)n- preferablybinds to R₁₀ or R₁₁. The divalent linking group is preferably analkylene group, an aralkylene group, an arylene group, or a divalentheterocyclic group, or a divalent linking group formed by binding anyone of an alkylene group, an aralkylene group, and an arylene group, andany one of —O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rc)-,—C(═O)N(Rd)-, —N(Rc)C(═O)—, —N(Rc)C(═O)O—, —N(Rc)C(═O)N(Rd)-, —SO—,—SO₂—, —SO₂N(Rc)-, and —N(Rc)SO₂—. Further preferable is an alkylenegroup, an aralkylene group, or an arylene group.

The preferable ranges of respective substituents of Formula (A1),Formula (B1), Formula (1-A1), Formula (1-B1), Formula (2-A1), Formula(2-B1), Formula (C1), and Formula (D1) will be described below; however,in a combination of a preferable range of each substituent with apreferable range of formulae, the respective more preferable ranges aremore preferable.

R₁ in Formula (A1) or Formula (B1) is preferably an alkyl group, an arylgroup, a heterocyclic group, a group represented by —Y₁—C(═X₃)—R₈ shownin Formula (1-A1), Formula (1-B1), Formula (2-A1), or Formula (2-B1), or—NH—C(═O)—R₁₀ or —NH—C(═O)—R₁₁ shown in Formula (C1) or Formula (D1);

further preferably a group represented by —Y₁—C(═X₃)—R₈ shown in Formula(1-A1), Formula (1-B1), Formula (2-A1), or Formula (2-B1), or—NH—C(═O)—R₁₀ or —NH—C(═O)—R₁₁ shown in Formula (C1) or Formula (D1);and

most preferably —NH—C(═O)—R₁₀ or —NH—C(═O)—R₁₁ shown in Formula (C1) andFormula (D1).

R₆ in Formula (A1) or Formula (B1) is an alkyl group, an aryl group, aheterocyclic group, a group represented by —Y₂—C(═X₄)—R₉ shown inFormula (1-A1), Formula (1-B1), Formula (2-A1), or Formula (2-B1), or—NH—C(═O)—R₁₁ shown in Formula (C1) or Formula (D1);

further preferably a group represented by —Y₂—C(═X₄)—R₉ shown in Formula(1-A1), Formula (1-B1), Formula (2-A1), or Formula (2-B1), or—NH—C(═O)—R₁₁ shown in Formula (C1) or Formula (D1); and

most preferably —NH—C(═O)—R₁₁ shown in Formula (C1) or Formula (D1).

The preferable ranges and examples of Y₁, X₃, Y₂, X₄, and R₈ to R₁₁ areas described below.

X₂ in Formula (A1) or Formula (B1) is preferably water, alcohols (e.g.methanol, ethanol, propanol), or a compound described in “Metal Chelate”[1] Takeichi Sakaguchi/Keihei Ueno (1995, Nankodo Co., Ltd.), the same[2] (1996), and the same [3] (1997), and further preferably water oralcohols, and most preferably p is 0.

In Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1), Formula(2-A1), Formula (2-B1), Formula (C1), or Formula (D1), Ra is preferablya halogen atom, an alkyl group, or an alkoxy group, and m is 0 or 1, andmost preferably is 0.

M in Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1), Formula(2-A1), Formula (2-B1), Formula (C1), or Formula (D1) is preferably ahydrogen atom, a trialkylamine having 3 to 14 carbon atoms, a quaternaryammonium having 4 to 20 carbon atoms, or an alkali metal, morepreferably a hydrogen atom, a trialkylamine having 3 to 9 carbon atoms,a quaternary ammonium salt having 4 to 8 carbon atoms, or an alkalimetal, further preferably a hydrogen atom.

L in Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1), Formula(2-A1), or Formula (2-B1) is preferably —O—, —N(Rb), —S—, or —SO₂— (inwhich Rb is a hydrogen atom or an alkyl group having 1 to 4 carbonatoms), more preferably —O—, —S—, or —SO₂—, and most preferably —S— orSO₂—.

Ma in Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1),Formula (2-A1), or Formula (2-B1) is preferably Fe, Zn, Co, V═O, or Cu,further preferably Zn, Co, V═O, or Cu, most preferably Zn.

R₂ and R₅ in Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1),Formula (2-A1), Formula (2-B1), Formula (C1), or Formula (D1) each arepreferably independently an alkyl group, an aryl group, a heterocyclicgroup, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group,a carboxyl group, an acyl group, a carbamoyl group, an alkylthio group,an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, anarylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinylgroup, an arylsulfinyl group, or a sulfamoyl group; more preferably aperfluoroalkyl group, an aryl group, a heterocyclic group, analkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, acarboxyl group, an acyl group, a carbamoyl group, an alkylsulfonylgroup, an arylsulfonyl group, a heterocyclic sulfonyl group, or asulfamoyl group; further preferably a perfluoroalkyl group, an arylgroup, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a cyano group, a carboxyl group, an acyl group, a carbamoylgroup, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoylgroup; and most preferably a perfluoroalkyl group, an alkoxycarbonylgroup, an aryloxycarbonyl group, a cyano group, a carbamoyl group, analkylsulfonyl group, or an arylsulfonyl group.

R₃ and R₄ in Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1),Formula (2-A1), Formula (2-B1), Formula (C1), or Formula (D1) are eachpreferably independently an alkyl group, an aryl group, a heterocyclicgroup, an alkoxycarbonyl group, a cyano group, or a carbamoyl group;more preferably an alkyl group, an aryl group, a heterocyclic group, ora cyano group; and most preferably an alkyl group, an aryl group, or aheterocyclic group.

R₇ in Formula (A1), Formula (B1), Formula (1-A1), Formula (1-B1),Formula (2-A1), Formula (2-B1), Formula (C1), or Formula (D1) ispreferably a hydrogen atom, a halogen atom, an alkyl group, an arylgroup, or a heterocyclic group; more preferably a hydrogen atom, analkyl group, an aryl group, or a heterocyclic group; further preferablya hydrogen atom, an alkyl group, or an aryl group; and most preferably ahydrogen atom.

X₁ in Formula (B1), Formula (1-B1), Formula (2-B1), or Formula (D1) ispreferably a halogen atom, an alkylcarbonyloxy group, an arylcarbonyloxygroup, a heterocyclic carbonyloxy group, a sulfonic acid group, analkylsulfonyloxy group, an arylsulfonyloxy group, or a phosphoric acidgroup; and more preferably a chlorine atom, an alkylcarbonyloxy group,an arylcarbonyloxy group, a sulfonic acid group, an alkylsulfonyloxygroup, or an arylsulfonyloxy group.

R₈ and R₉ in Formula (1-A1), Formula (1-B1), Formula (2-A1), and Formula(2-B1) each are preferably independently an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an alkoxy group, an aminogroup, or an anilino group; more preferably an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group; further preferably analkyl group, an alkenyl group or an aryl group; and most preferably analkyl group or an aryl group.

X₃ and X₄ in Formula (1-A1), Formula (1-B1), Formula (2-A1), or Formula(2-B1) each are preferably independently NR (in which R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group), a nitrogen atom, or an oxygen atom; more preferably—NH—, a nitrogen atom, or an oxygen atom; and most preferably an oxygenatom.

Y₁ and Y₂ in Formula (1-A1), Formula (1-B1), Formula (2-A1), or Formula(2-B1) each are preferably independently NR (in which R is a hydrogenatom, an alkyl group, an alkenyl group, an aryl group, a heterocyclicgroup, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group),more preferably NR (in which R is a hydrogen atom, or an alkyl group),and most preferably a —NH— group.

R₁₀ and R₁₁ in Formula (C1) or Formula (D1) each are preferablyindependently an alkyl group, an aryl group, or a heterocyclic group,and more preferably an alkyl group or an aryl group.

It is a preferably exemplary embodiment of Formula (C1) or Formula (D1),in which R₂ and R₅ each are independently a perfluoroalkyl group, anaryl group, a heterocyclic group, an alkoxycarbonyl group, anaryloxycarbonyl group, a cyano group, a carboxyl group, an acyl group, acarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or asulfamoyl group (most preferably a perfluoroalkyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, acarbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group); R₃and R₄ are each independently an alkyl group, an aryl group, aheterocyclic group, or a cyano group (most preferably, an alkyl group,an aryl group, or a heterocyclic group); R₇ is a hydrogen atom, an alkylgroup, or an aryl group (most preferably a hydrogen atom); X₁ is achlorine atom, an alkylcarbonyloxy group, an arylcarbonyloxy group, asulfonic acid group, an alkylsulfonyloxy group, or an arylsulfonyloxygroup; R₁₀ and R₁₁ are each independently an alkyl group, an aryl group,or a heterocyclic group (more preferably an alkyl group or an arylgroup); M is a hydrogen atom, a trialkylamine having 3 to 9 carbonatoms, a quaternary ammonium salt having 4 to 8 carbon atoms, or analkali metal (further preferably a hydrogen atom); Ra is a halogen atom,an alkyl group, or an alkoxy group; m is 0 or 1 (most preferably m is0); and n is 0 or 2.

Next, examples of the compounds represented by Formula (A1), Formula(B1), Formula (1-A1), Formula (1-B1), Formula (2-A1), Formula (2-B1),Formula (C1), or Formula (D1) are shown below, but the invention is notlimited by them.

R³, R⁴ R⁸ R⁹ A-1 —CH₃ —CH₃

A-2 Same as above

Same as above A-3 Same as above —(t)C₄H₉ Same as above A-4 Same as above

Same as above A-5 Same as above —C₁₂H₂₅ Same as above A-6 Same as above—CH₂OCH₃ Same as above A-7 Same as above —CH₂CH₂COOC₂H₅ Same as aboveA-8 Same as above —CH₂OCH₂COOC₂H₅ Same as above A-9 Same as above

Same as above

R³, R⁴ R⁸ R⁹ A-10 —CH₃

A-11 Same as above

Same as above A-12 Same as above

Same as above A-13 Same as above

Same as above A-14 Same as above —CH₂OCH₂COOH Same as above A-15 Same asabove

Same as above

R³, R⁴ R⁸ R⁹ A-16 —CH₃ —CF₃

A-17 Same as above —OC₂H₅ Same as above A-18 Same as above —NHC₄H₉ Sameas above A-19 —C₂H₅ —(t)C₄H₉ Same as above A-20

Same as above A-21 —CH₃ Same as above

R³, R⁴ R⁸ R⁹ A-22 —CH₃ —(t)C₄H₉

A-23 Same as above Same as above

A-24

—CH₃

A-25 Same as above —(t)C₄H₉ Same as above A-26 Same as above

Same as above

R³, R⁴ R⁸ R⁹ A-27

—(t)C₄H₉

A-28

Same as above Same as above A-29

Same as above Same as above A-30

Same as above Same as above A-31

Same as above —(t)C₄H₉

R³, R⁴ R⁸ R⁹ A-32 —CH₃ —(t)C₄H₉

A-33

Same as above Same as above A-34 —CH₃ —CH₃

A-35 Same as above —(t)C₄H₉

A-36 Same as above

Same as above

R³, R⁴ R⁸ R⁹ A-37 —CH₃ —(t)C₄H₉

A-38 Same as above Same as above

A-39 Same as above Same as above

A-40 Same as above

R³, R⁴ R⁸ R⁹ A-41 —(t)C₄H₉ —(t)C₄H₉

A-42

—CH₃

A-43

Same as above Same as above A-44 Same as above —(t)C₄H₉ Same as aboveA-45 —CH₃

Same as above A-46

—CH₃ Same as above

R³, R⁴ R⁸ R⁹ B-1

B-2 Same as above Same as above

B-3 Same as above

Same as above B-4 Same as above

Same as above B-5 Same as above

Same as above

R³, R⁴ R⁸ R⁹ B-6

B-7 Same as above

Same as above B-8 Same as above

B-9 Same as above

Same as above

R³, R⁴ R⁸ R⁹ B-10

B-11

Same as above Same as above B-12

Same as above Same as above

R³ R⁴ R⁸ R⁹ C-1 —CH₃

—(t)C₄H₉

C-2 Same as above Same as above Same as above

C-3 Same as above Same as above Same as above

C-4 Same as above

Same as above Same as above

R³ R⁴ R⁸ R⁹ C-5 —CH₃

C-6 Same as above Same as above

Same as above C-7 Same as above Same as above

C-8 Same as above Same as above

Same as above

R³ R⁴ R⁸ R⁹ C-9  —CH₃

C-10 —CF₃ Same as above Same as above Same as above C-11

Same as above

R³ R⁴ R⁸ R⁹ D-1

D-2 Same as above Same as above

D-3 Same as above Same as above

Same as above D-4 Same as above Same as above Same as above

R³ R⁴ R⁸ R⁹ D-5

D-6 Same as above Same as above

D-7 Same as above Same as above Same as above

D-8 Same as above Same as above Same as above

R³ R⁴ R⁸ R⁹ D-9 

D-10 Same as above Same as above Same as above —(t)C₄H₉ D-11

—CH₃ —(t)C₄H₉

R³ R⁴ R⁸ R⁹ D-12

—CH₃ —(t)C₄H₉

D-13

Same as above Same as above

R³ R⁴ R⁸ R⁹ E-1

—(t)C₄H₉

E-2 Same as above Same as above Same as above

E-3 Same as above Same as above Same as above

E-4 Same as above Same as above

Same as above

R³ R⁴ R⁸ R⁹ E-5

E-6 Same as above Same as above

Same as above E-7 Same as above Same as above

Same as above E-8 Same as above Same as above

Same as above E-9 Same as above Same as above

Same as above

R³ R⁴ R⁸ R⁹ E-10

E-11 Same as above Same as above

Same as above E-12 Same as above Same as above

Same as above

R² R³ R⁴ R⁵ R⁸ F-1

—CH₃ —CH₃ —SO₂CH₃ —(t)C₄H₉ F-2 Same as above Same as above Same as above

Same as above F-3 Same as above

Same as above Same as above F-4 Same as above Same as above Same asabove Same as above

R² R³ R⁴ R⁵ R⁸ F-5  —SO₂CH₃

F-6  Same as above Same as above Same as above Same as above —(t)C₄H₉F-7  Same as above —CH₃ —CH₃ Same as above Same as above F-8 

Same as above Same as above Same as above Same as above F-9 

Same as above Same as above F-10

Same as above Same as above Same as above Same as above

R² R³ R⁴ R⁵ R⁸ F-11 —COOC₂H₅

—(t)C₄H₉ F-12

Same as above Same as above Same as above Same as above F-13

Same as above Same as above Same as above Same as above F-14 Same asabove Same as above —CH₃ Same as above Same as above

Compounds of Formula (A1), Formula (B1), Formula (C1), or Formula (D1)may be synthesized by the method described in US Application PublicationNo. 2008/0076044 A1.

The colored curable composition according to the first exemplaryembodiment of the invention includes at least one compound selected fromthe compounds of Formula (A1) and Formula (B1) and tautomers thereof,and more preferably at least one compound selected from the compounds ofFormula (C1) and Formula (D1) and tautomers thereof, and two or more ofthe compounds and tautomers may be used in combination.

The amount of at least one compound selected from the compounds ofFormula (A1) and Formula (B1), which is included in the colored curablecomposition of the first exemplary embodiment of the invention, variesdepending on a molecular weight and a molar absorption coefficientthereof, and is preferably from 0.5 to 80% by mass, more preferably from0.5 to 60% by mass, and most preferably from 0.5 to 50% by mass, withrespect to the total solid contents of the colored curable composition.

The colored curable composition according to the first exemplaryembodiment of the invention and the color filter using the coloredcurable composition may include a phthalocyanine compound such as thosedisclosed in US Application Publication No. 2008/0076044 A1, atriarylmethane coloring agent having an absorption maximum at 550 to 650nm such as C.I. Acid Blue 7, C.I. Acid Blue 83, C.I. Acid Blue 90, C.I.Solvent Blue 38, C.I. Acid Violet 17, C.I. Acid Violet 49 or C.I. AcidGreen 3, in addition to the compounds of Formula (A1), Formula (B1),Formula (C1), and Formula (D1) and tautomers thereof.

Further, a xanthene colorant having an absorption maximum at 500 nm to600 nm, for example, C. I. Acid. Red 289 may also be used.

The phthalocyanine coloring agent or the triarylmethane coloring agentmay be used as long as the effect of the invention is not deteriorated,and the amount thereof is preferably from 0.5 to 50% by mass withrespect to the total solid contents of the colored curable compositionof the invention.

In order to manufacture a blue filter array, it is preferable that amixture of a metal complex of the invention and at least one of thephthalocyanine coloring agents is used.

In this case, a proportion of them within the mixture varies dependingon their molar absorption coefficients, spectrometric propertiesrequired, film thickness, and the like. Generally, the proportion (i.e.,total amount of metal complex of the invention: phthalocyanine coloringagent) is from 10:1 to 1:20, and preferably in a range of from 5:1 to1:10.

Colored Curable Composition of Second Exemplary Embodiment

The colored curable composition according to a second exemplaryembodiment of the invention includes, as a coloring agent, at least oneselected from the group consisting of a compound represented by Formula(A2), a compound represented by Formula (B2), and a tautomer thereof.

It is preferable that the colored curable composition according to thesecond exemplary embodiment of the invention is an ultraviolet-sensitivecolored curable composition.

In Formula (A2) and Formula (B2), R₁ to R₆ each independently representa hydrogen atom or a substituent, and R₇ represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, or a heterocyclic group,provided that any one of the substituents represented by R₁ to R₆ is adivalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M. Mrepresents a hydrogen atom, or an organic base or metal atom necessaryfor neutralizing a charge. L represents an alkylene group, an aralkylenegroup, or an arylene group, or a divalent group which may be formed by acombination of divalent groups selected from the group consisting of analkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO₂—,—N(Ra)—, —COO—, —OCO—, —CON(Rb)—, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—,—N(Rb)CON(Rc)—, —SO₂N(Rb)—, and —N(Rb)SO₂—. Ra represents an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group, or an arylsulfonyl group; and Rb and Rceach independently represent a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group.

Ma represents a metal or a metal compound which may form a complex; X₁represents a group necessary for neutralizing a charge; X₂ represents agroup which may bind to Ma; and p represents 0 or 1. In Formula (B2), X₁and X₂ may bind together to form a 5-membered, 6-membered, or 7-memberedring.

The compounds represented by Formula (A2) and Formula (B2),respectively, will be described in detail.

In a compound represented by Formula (A2) or Formula (B2), any one ofthe substituents represented by R₁ to R₆ is a divalent linking groupthat binds to -(L)-SO₃ ⁻ or -(L)SO₃M, and explanation of any divalentgroup of R₁ to R₆ is expressed by substitution with a hydrogen atom for-(L)-SO₃—, and -(L)-SO₃M.

R¹ to R⁶ in Formula (A2) or Formula (B2) each independently represents ahydrogen atom or a substituent. Examples of the substituent representedby any one of R¹ to R⁶ include a halogen atom (for example, fluorine,chlorine, bromine), an alkyl group (for example, a straight, branched orcyclic alkyl group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include a methylgroup, an ethyl group, a propyl group, an isopropyl group, a butylgroup, a t-butyl group, a pentyl group, a hexyl group, a heptyl group,an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecylgroup, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a1-norbornyl group, and a 1-adamantyl group), an alkenyl group (forexample, an alkenyl group having preferably 2 to 48 carbon atoms, morepreferably 2 to 18 carbon atoms; examples thereof include a vinyl group,an allyl group, and a 3-buten-1-yl group), an aryl group (for example,an aryl group having preferably 6 to 48 carbon atoms, more preferably 6to 24 carbon atoms; examples thereof include a phenyl group and anaphthyl group), a heterocyclic group (for example, a heterocyclic grouphaving preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbonatoms; examples thereof include a 2-thienyl group, a 4-pyridyl group, a2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and abenzotriazol-1-yl group), a silyl group (for example, a silyl grouphaving preferably 3 to 38 carbon atoms, more preferably 3 to 18 carbonatoms; examples thereof include a trimethylsilyl group, a triethylsilylgroup, a tributylsilyl group, a t-butyldimethylsilyl group, and at-hexyldimethylsilyl group), a hydroxyl group, a cyano group, a nitrogroup, an alkoxy group (for example, an alkoxy group having preferably 1to 48 carbon atoms, more preferably 1 to 24 carbon atoms; examplesthereof include a methoxy group, an ethoxy group, a 1-butoxy group, a2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxygroup, and a cycloalkyloxy group such as a cyclopentyloxy group or acyclohexyloxy group), an aryloxy group (for example, an aryloxy grouphaving preferably 6 to 48 carbon atoms, more preferably 6 to 24 carbonatoms; examples thereof include a phenoxy group and a 1-naphthoxygroup), a heterocyclic oxy group (for example, a heterocyclic oxy grouphaving preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbonatoms; examples thereof include a 1-phenyltetrazol-5-oxy group and a2-tetrahydropyranyloxy group), a silyloxy group (for example, a silyloxygroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms; examples thereof include a trimethylsilyloxy group, at-butyldimethylsiliyloxy group, and a diphenylmethylsilyloxy group), anacyloxy group (for example, an acyloxy group having preferably 2 to 48carbon atoms, more preferably 2 to 24 carbon atoms; examples thereofinclude an acetoxy group, a pivaloyloxy group, a benzoyloxy group, and adodecanoyloxy group), an alkoxycarbonyloxy group (for example, analkoxycarbonyloxy group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms; examples thereof include anethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and acycloalkyloxycarbonyloxy group such as a cyclohexyloxycarbonyloxygroup), an aryloxycarbonyloxy group (for example, an aryloxycarbonyloxygroup having preferably 7 to 32 carbon atoms, more preferably 7 to 24carbon atoms; examples thereof include a phenoxycarbonyloxy group), acarbamoyloxy group (for example, a carbamoyloxy group having preferably1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms; examplesthereof include a N,N-dimethylcarbamoyloxy group, a N-butylcarbamoyloxygroup, N-phenylcarbamoyloxy group, and a N-ethyl-N-phenylcarbamoyloxygroup), a sulfamoyloxy group (for example, a sulfamoyloxy group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms;examples thereof include a N,N-diethylsulfamoyloxy group and aN-propylsulfamoyloxy group),

an alkylsulfonyloxy group (for example, an alkylsulfonyloxy group havingpreferably 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms;examples thereof include a methylsulfonyloxy group, ahexadecylsulfonyloxy group, and a cyclohexylsulfonyloxy group), anarylsulfonyloxy group (for example, an arylsulfonyloxy group havingpreferably 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms;examples thereof include a phenylsulfonyloxy group), an acyl group (forexample, an acyl group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include a formylgroup, an acetyl group, a pivaloyl group, a benzoyl group, atetradecanoyl group, and a cyclohexanoyl group), an alkoxycarbonyl group(for example, an alkoxycarbonyl group having preferably 2 to 48 carbonatoms, more preferably 2 to 24 carbon atoms; examples thereof include amethoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonylgroup, a cyclohexyloxycarbonyl group, and a2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), anaryloxycarbonyl group (for example, an aryloxycarbonyl group havingpreferably 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms;examples thereof include a phenoxycarbonyl group), a carbamoyl group(for example, a carbamoyl group having preferably 1 to 48 carbon atoms,more preferably 1 to 24 carbon atoms; examples thereof include acarbamoyl group, a N,N-diethylcarbamoyl group, aN-ethyl-N-octylcarbamoyl group, a N,N-dibutylcarbamoyl group, aN-propylcarbamoyl group, a N-phenylcarbamoyl group, aN-methyl-N-phenylcarbamoyl group, and a N,N-dicyclohexylcarbamoylgroup), an amino group (for example, an amino group having preferably 32or less carbon atoms, more preferably 24 or less carbon atoms; examplesthereof include an amino group, a methylamino group, a N,N-dibutylaminogroup, a tetradecylamino group, a 2-ethylhexylamino group, and acyclohexylamino group), an anilino group (for example, an anilino grouphaving preferably 6 to 32 carbon atoms, more preferably 6 to 24 carbonatoms; examples thereof include an anilino group and a N-methylanilinogroup), a heterocyclic amino group (for example, a heterocyclic aminogroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms; examples thereof include a 4-pyridyl amino group), acarbonamido group (for example, a carbonamido group having preferably 2to 48 carbon atoms, more preferably 2 to 24 carbon atoms; examplesthereof include an acetamide group, a benzamide group, atetradecaneamido group, a pivaloylamido group, and a cyclohexaneamidogroup), a ureido group (for example, a ureido group having preferably 1to 32 carbon atoms, more preferably 1 to 24 carbon atoms; examplesthereof include a ureido group, a N,N-dimethylureido group, and aN-phenylureido group), an imido group (for example, an imido grouphaving preferably 36 or less carbon atoms, more preferably 24 or lesscarbon atoms; examples thereof include a N-succinimido group and aN-phthalimido group), an alkoxycarbonylamino group (for example, analkoxycarbonylamino group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms; examples thereof include amethoxycarbonylamino group, an ethoxycarbonylamino group, at-butoxycarbonylamino group, an octadecyloxycarbonylamino group, and acyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (forexample, an aryloxycarbonylamino group having preferably 7 to 32 carbonatoms, more preferably 7 to 24 carbon atoms; examples thereof include aphenoxycarbonylamino group), a sulfonamido group (for example, asulfonamido group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include amethanesulfonamido group, a butanesulfonamido group, abenzenesulfonamido group, a hexadecanesulfonamido group, and acyclohexanesulfonamido group), a sulfamoylamino group (for example, asulfamoylamino group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include aN,N-dipropylsulfamoylamino group and a N-ethyl-N-dodecylsulfamoylaminogroup), an azo group (for example, an azo group having preferably 1 to32 carbon atoms, more preferably 1 to 24 carbon atoms; examples thereofinclude a phenylazo group and a 3-pyrazolylazo group), an alkylthiogroup (for example, an alkylthio group having preferably 1 to 48 carbonatoms, more preferably 1 to 24 carbon atoms; examples thereof include amethylthio group, an ethylthio group, an octylthio group, and acyclohexylthio group),

an arylthio group (for example, an arylthio group having preferably 6 to48 carbon atoms, more preferably 6 to 24 carbon atoms; examples thereofinclude a phenylthio group), a heterocyclic thio group (for example, aheterocyclic thio group having preferably 1 to 32 carbon atoms, morepreferably 1 to 18 carbon atoms; examples thereof include a2-benzothiazolylthio group, a 2-pyridylthio group, and a1-phenyltetrazolylthio group), an alkylsulfinyl group (for example, analkylsulfinyl group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include adodecanesulfinyl group), an arylsulfinyl group (for example, anarylsulfinyl group having preferably 6 to 32 carbon atoms, morepreferably 6 to 24 carbon atoms; examples thereof include aphenylsulfinyl group), an alkylsulfonyl group (for example, analkylsulfonyl group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include amethylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, abutylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonylgroup, a hexadecylsulfonyl group, an octylsulfonyl group, and acyclohexylsulfonyl group), an arylsulfonyl group (for example, anarylsulfonyl group having preferably 6 to 48 carbon atoms, morepreferably 6 to 24 carbon atoms; examples thereof include aphenylsulfonyl group and a 1-naphthylsulfonyl group), a sulfamoyl group(for example, a sulfamoyl group having preferably 32 or less carbonatoms, more preferably 24 or less carbon atoms; examples thereof includea sulfamoyl group, a N,N-dipropylsulfamoyl group, aN-ethyl-N-dodecylsulfamoyl group, a N-ethyl-N-phenylsulfamoyl group, anda N-cyclohexylsulfamoyl group), a sulfo group, a phosphonyl group (forexample, a phosphonyl group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include aphenoxyphosphonyl group, an octyloxyphosphonyl group, and aphenylphosphonyl group), a phosphinoylamino group (for example, aphosphinoylamino group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms; examples thereof include adiethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group).

When the substituents represented by R₁ to R₆ in Formula (A2) or Formula(B2) may each further have at least one additional substituent, theadditional substituent may be any one of the substituents represented byR₁ to R₆. When the substituents represented by R₁ to R₆ in Formula (A2)or Formula (B2) is each substituted with two or more additionalsubstituents, the additional substituents may be the same as ordifferent from each other, provided that any one of the substituentsrepresented by R₁ to R₆ is a divalent linking group that binds to-(L)-SO₃ ⁻ or -(L)-SO₃M.

When any one of the substituents represented by R₁ to R₆ is a divalentlinking group, the divalent linking group may be a new divalent linkinggroup formed by binding at least two substituents. For example, the newdivalent linking group may be formed by binding at least two divalentlinking groups selected from the group consisting of an alkylene group,an aralkylene group, an arylene group, a divalent heterocyclic group,—O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rd)—, —C(═O)N(Rd)—,—N(Rd)C(═O)—, —N(Rd)C(═O)O—, —N(Rd)C(═O)N(Re)—, —C(═O)N(Rd)C(═O)—, —SO—,—SO₂—, —SO₃—, —SO₂N(Rd)—, —N(Rd)SO₂—, —C(═O)N(Rd)SO₂—, and—SO₂N(Rd)SO₂—.

Rd and Re each independently represent a hydrogen atom, an alkyl group,an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,or a sulfamoyl group. These alkyl group, aryl group, heterocyclic group,acyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonylgroup, carbamoyl group, and sulfamoyl group may each be substituted withan additional group which is any one of the substituents represented byR₁ to R₆, and when they are each substituted with 2 or moresubstituents, the additional substituents may be the same as ordifferent from each other.

R₇ in Formula (A2) or Formula (B2) represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group, or a heterocyclic group. Thehalogen group, the alkyl group, the aryl group, and the heterocyclicgroup of R₇ have the same meanings as the halogen atom, the alkyl group,the aryl group, and the heterocyclic group represented by any of R₁ toR₆, and the preferable ranges and examples thereof are also the same.

M in Formula (A2) or Formula (B2) represents a hydrogen atom, or anorganic base or metal atom necessary for neutralizing a charge. Examplesof the organic base include alkylamines, anilines, quaternary amines,guanidines, pyridines, and quinolines. Examples of the metal atominclude alkali metal atoms. As M in Formula (A2) or Formula (B2),ammonia is also preferable. M is most preferably a hydrogen atom.

L in Formula (A2) or Formula (B2) represents an alkylene group, anaralkylene group, or an arylene group, or a divalent group which may beformed by a combination of divalent groups selected from the groupconsisting of an alkylene group, an aralkylene group, an arylene group,—O—, —S—, —SO₂—, —N(Ra)—, —COO—, —OCO—, —CON(Rb)—, —N(Rb)CO—,—N(Rb)COO—, —OOCN(Rb)—, —N(Rb)CON(Rc)—, —SO₂N(Rb)—, and —N(Rb)SO₂—. Rarepresents an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group, and Rb and Rc each independently represent ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, or aheterocyclic group.

The alkylene group represented by L is a straight, branched or cyclicalkylene group having preferably 1 to 18 carbon atoms, more preferably 1to 12 carbon atoms, and examples thereof include a methylene group, anethylene group, a propylene group, a butylene group, a cyclopropylenegroup, a cyclobutylene group, and a cyclohexylene group. The aralkylenegroup represented by L is an aralkylene group having preferably 7 to 18carbon atoms, more preferably 7 to 16 carbon atoms, and examples thereofinclude a benzylene group and a phenethylene group. The arylene grouprepresented by L is an arylene group having preferably 6 to 18 carbonatoms, more preferably 6 to 12 carbon atoms, and examples thereofinclude an o-phenylene group, a m-phenylene group, a p-phenylene group,and a 1,4-naphthylene group.

When the alkylene group, aralkylene group, or arylene group representedby L further has at least one additional substituent, the additionalsubstituent may be any one of the substituents represented by R₁ to R₆,and when it is substituted with two or more additional substituents, theadditional substituents may be the same as or different from each other.

L may be a divalent group formed by a combination of divalent groupsselected from the group consisting of an alkylene group, an aralkylenegroup, an arylene group, —O—, —S—, —SO₂—, —N(Ra)-, —COO—, —OCO—,—CON(Rb)-, —N(Rb)CO—, —N(Rb)COO—, OOCN(Rb)-, —N(Rb)CON(Rc)-, —SO₂N(Rb)-,and —N(Rb)SO₂—. However, —O—, —S—, —SO₂—, —N(Ra)-, —COO—, —OCO—,—CON(Rb)-, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)-, —N(Rb)CON(Rc)-,—SO₂N(Rb)-, or —N(Rb)SO₂— does not directly bind to a —SO₃ ⁻ or —SO₃Mgroup, and —SO₃ ⁻ or —SO₃M binds via the alkylene group, the aralkylenegroup, or the arylene group.

The alkyl group, the alkenyl group, the aryl group, the heterocyclicgroup, the acyl group, the alkylsulfonyl group, and the arylsulfonylgroup represented by Ra have the same meanings as the alkyl group, thealkenyl group, the aryl group, the heterocyclic group, the acyl group,the alkylsulfonyl group, and the arylsulfonyl group represented by eachof R₁ to R₆, and the preferable ranges and examples thereof are also thesame.

When the alkyl group, the alkenyl group, the aryl group, theheterocyclic group, the acyl group, the alkylsulfonyl group, and thearylsulfonyl group represented by Ra each have at least one additionalsubstituent, the additional substituent may be any one of thesubstituents represented by R₁ to R₆, and when they each are substitutedwith two or more additional substituents, the additional substituentsmay be the same as or different from each other.

The alkyl group, the alkenyl group, the aryl group, and the heterocyclicgroup represented by Rb have the same meanings as the alkyl group, thealkenyl group, the aryl group, and the heterocyclic group represented byR₁ to R₆, and the preferable ranges and examples thereof are also thesame.

When the alkyl group, the alkenyl group, the aryl group, or theheterocyclic group represented by Rb has at least one additionalsubstituent, the additional substituent may be any one of thesubstituents represented by R₁ to R₆, and when it is substituted withtwo or more additional substituents, the additional substituents may bethe same as or different from each other.

Ma in Formula (A2) or Formula (B2) represents a metal or a metalcompound which may form a complex. Examples of the metal and metalcompound represented by Ma include divalent metal atoms, divalent metaloxides, divalent metal hydroxides, and divalent metal chlorides. Forexample, Ma may be any one of Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb,Cu, Ni, Co, and Fe, a metal chloride such as AlCl, InCl, FeCl, TiCl₂,SnCl₂, SiCl₂, or GeCl₂, a metal oxide such as TiO or VO, or a metalhydroxide such as Si(OH)₂.

Among them, from the viewpoints of stability, spectrometric property,heat resistance, light resistance, and production suitability of thecomplex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO ispreferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is morepreferable, Fe, Zn, Co, or Cu is further preferable, and Zn is mostpreferable.

In Formula (A2) or Formula (B2), X₁ represents a group necessary forneutralizing a charge; X₂ represents a group which may bind to Ma; and prepresents 0 or 1. X₁ and X₂ may bind together to form a 5-membered,6-membered, or 7-membered ring.

X₁ in Formula (B2) represents a group necessary for neutralizing acharge, and examples thereof include a halogen, a hydroxy group, acarboxylic acid group, a phosphoric acid group, and a sulfonic acidgroup.

X₂ in Formula (A2) or Formula (B2) may be any group as long as it is agroup which may bind to Ma, and examples thereof include water, alcohols(e.g. methanol, ethanol, propanol), and compounds described in “MetalChelate” [1] Takeichi Sakaguchi, Keihei Ueno (1995, Nankodo Co., Ltd.),[2] (1996), and [3] (1997).

In Formula (A2) or Formula (B2), p represents 0 or 1.

X₁ and X₂ in Formula (A2) or Formula (B2) may bind to each other to forma 5-membered, 6-membered, or 7-membered ring with Ma. The 5-membered,6-membered, or 7-membered ring may be a saturated or unsaturated ring.The 5-membered, 6-membered or 7-membered ring may contain only carbonatoms or may be a heterocyclic ring having at least one atom selectedfrom nitrogen, oxygen and sulfur atoms.

From the viewpoints of synthesis suitability, and stability and fastnessof a compound, the compound represented by Formula (A2) or Formula (B2),or the tautomer thereof is preferably a dipyrromethene metal complexrepresented by Formula (1-A2) or Formula (1-B2), or a tautomer thereof.

In Formulas (1-A2) and (1-B2), R₂ to R₅ each independently represent ahydrogen atom or a substituent; R₇ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group, or a heterocyclic group; and R₈ andR₉ each independently represent an alkyl group, an alkenyl group, anaryl group, a heterocyclic group, an alkoxy group, an aryloxy group, anamino group, an anilino group or a heterocyclic amino group; providedthat any one of the substituents represented by R₂ to R₅, R₈ and R₉ is adivalent linking group to bind to -(L)-SO₃ ⁻ or -(L)-SO₃M. M representsa hydrogen atom, or an organic base or metal atom necessary forneutralizing a charge. L represents an alkylene group, an aralkylenegroup, or an arylene group, or a divalent group which may be formed by acombination of divalent groups selected from the group consisting of analkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO₂—,—N(Ra)—, —COO—, —OCO—, —CON(Rb)—, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—,—N(Rb)CON(Rc)—, —SO₂N(Rb)—, and —N(Rb)SO₂—. Ra represents an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rceach independently represent a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group.

Ma represents a metal or metal compound which may form a complex, and X₁represents a group necessary for neutralizing a charge of Ma. X₃ and X₄each independently represent NR (in which R represents a hydrogen atom,an alkyl group, an alkenyl group, an aryl group, a heterocyclic group,an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; R andR₈ or R₉ may bind together to form a 5-membered, 6-membered, or7-membered ring), an oxygen atom, or a sulfur atom; Y₁ and Y₂ eachindependently represent NR (in which R represents a hydrogen atom, analkyl group, an alkenyl group, an aryl group, a heterocyclic group, anacyl group, an alkylsulfonyl group, or an arylsulfonyl group) or anoxygen atom; R₈ and Y₁ may bind together to form a 5-membered,6-membered, or 7-membered ring; and R₉ and Y₂ may bind together to forma 5-membered, 6-membered, or 7-membered ring.

Next, Formula (1-A2) and Formula (1-B2) will be described in detail.

R₂ to R₅, R₇, M, L, Ma, and X₁ of Formula (1-A2) and Formula (1-B2) havethe same meanings as those of Formula (A2) and Formula (B2), and thepreferable ranges and examples thereof are also the same.

When any one of R₈ and R₉ in Formula (1-A2) or Formula (1-B2) is adivalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M, thedivalent linking group of R₈ or R₉ will be explained by substitutionwith a hydrogen atom for -(L)-SO₃ ⁻ or -(L)-SO₃M.

R₈ and R₉ in Formula (1-A2) and Formula (1-B2) each independentlyrepresent an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an alkoxy group, an aryloxy group, an amino group,an anilino group, or a heterocyclic amino group.

The preferable ranges and examples of the alkyl group, the alkenylgroup, the aryl group, the heterocyclic group, the alkoxy group, thearyloxy group, the amino group, the anilino group, and the heterocyclicamino group represented by each of R₈ and R₉ are the same as those of R₁to R₆.

The alkyl group, the alkenyl group, the aryl group, the heterocyclicgroup, the alkoxy group, the aryloxy group, the amino group, the anilinogroup, and the heterocyclic amino group represented by R₈ and R₉ mayeach further have at least one additional substituent which is any oneof the substituents represented by R₁ to R₆, and when they aresubstituted with two or more additional substituents, the additionalsubstituents may be the same as or different from each other.

When any one of the substituents represented by R₈ and R₉ is a divalentlinking group, the divalent linking group may be a new divalent linkinggroup formed by binding at least two substituents. For example, the newdivalent linking group may be formed by binding at least two divalentlinking groups selected from the group consisting of an alkylene group,an aralkylene group, an arylene group, a divalent heterocyclic group,—O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—, —OC(═O)N(Rd)—, —C(═O)N(Rd)—,—N(Rd)C(═O)—, —N(Rd)C(═O)O—, —N(Rd)C(═O)N(Re)—, —SO—, —SO₂—, —SO₃—,—SO₂N(Rd)—, —N(Rd)SO₂—, —C(═O)N(Rd)SO₂—, and —SO₂N(Rd)SO₂—.

Rd and Re each independently represent a hydrogen atom, an alkyl group,an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,or a sulfamoyl group. These alkyl group, aryl group, heterocyclic group,acyl group, alkoxycarbonyl group, alklysulfonyl group, arylsulfonylgroup, carbamoyl group, and sulfamoyl group may be substituted with anadditional group which is any one of the substituents represented by R₁to R₆, and when they are each substituted with two or more additionalsubstituents, the additional substituents may be the same as ordifferent from each other.

X₃ and X₄ in Formula (1-A2) or Formula (1-B2) each independentlyrepresent NR (in which R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; and R and R₈ or R₉ may betaken together to form a 5-membered, 6-membered, or 7-membered ring), anoxygen atom, or a sulfur atom. The preferable ranges and examples of thealkyl group, the alkenyl group, the aryl group, the heterocyclic group,the acyl group, the alkylsulfonyl group, and the arylsulfonyl grouprepresented by R are the same as those of the alkyl group, the alkenylgroup, the aryl group, the heterocyclic group, the acyl group, thealkylsulfonyl group, and the arylsulfonyl group represented by any of R₁to R₆.

When R is substituted with at least one additional substituent, theadditional substituent may be any one of the substituents represented byR₁ to R₆, and when it is substituted with two or more additionalsubstituents, the additional substituents may be the same as ordifferent from each other.

X₃ and X₄ each preferably represent NR (in which R is a hydrogen atom,an alkyl group, an aryl group, an alkylsulfonyl group, or anarylsulfonyl group) or an oxygen atom, and, from the viewpoints ofsynthesis suitability and stability of a compound, an oxygen atom ismost preferable.

Y₁ and Y₂ in Formula (1-A2) or Formula (1-B2) each independentlyrepresent NR (in which R is a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group) or an oxygen atom, and Rin NR has the same meaning as that of R in NR as an example of X₃ andX₄.

In Formula (1-A2) or Formula (1-B2), R₈ and Y₁ may bind together to forma 5-membered, 6-membered, or 7-membered ring, and R₉ and Y₂ may bindtogether to form a 5-membered, 6-membered, or 7-membered ring.

Ma represents a metal or metal compound which may form a complex, and X₁represents a group necessary for neutralizing a charge of Ma.

From the viewpoints of synthesis suitability, and stability, andsolubility in an organic solvent of a compound, Formula (1-A2) isfurther preferably represented by the following Formula (C2) or atautomer thereof, and Formula (1-B2) is further preferably representedby the following Formula (D2) or a tautomer thereof.

In Formula (C2) and Formula (D2), R₂ to R₅ each independently representa hydrogen atom or a substituent; R₇ represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, or a heterocyclic group;and R₁₀ and R₁₁ each independently represent an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an alkoxy group, an aryloxygroup, an amino group, an anilino group, or a heterocyclic amino group;provided that any one of the substituents represented by R₂ to R₅, R₁₀and R₁₁ is a divalent linking group that binds to -(L)-SO₃ ⁻ or-(L)-SO₃M. M represents a hydrogen atom, or an organic base or metalatom necessary for neutralizing a charge. L represents an alkylenegroup, an aralkylene group, or an arylene group, or a divalent groupwhich may be formed by a combination of divalent groups selected fromthe group consisting of an alkylene group, an aralkylene group, anarylene group, —O—, —S—, —SO₂—, —N(Ra)—, —COO—, —OCO—, —CON(Rb)—,—N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—, —N(Rb)CON(Rc)—, —SO₂N(Rb)—, and—N(Rb)SO₂—. Ra represents an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an acyl group, an alkylsulfonyl group, oran arylsulfonyl group, and Rb and Rc each independently represent ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, or aheterocyclic group. X₁ represents a group necessary for neutralizing acharge of Zn.

R₂ to R₅, R₇, M, L, and X₁ in Formula (C2) or Formula (D2) have the samemeanings as in Formula (A2), Formula (B2), Formula (1-A2), and Formula(1-B2), and the preferable ranges and examples thereof are also thesame.

R₁₀ and R₁₁ each independently represent an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an alkoxy group, an aryloxygroup, an amino group, an anilino group, or a heterocyclic amino group,provided that any one of the substituents represented by R₂ to R₅, R₁₀,and R₁₁ is a divalent linking group that binds to -(L)-SO₃ ⁻ or-(L)-SO₃M.

When any one of R₁₀ and R₁₁ in Formula (C2) or Formula (D2) is adivalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M, thedivalent linking group represented by R₁₀ or R₁₁ is explained bysubstitution with a hydrogen atom for -(L)-SO₃ ⁻ or -(L)-SO₃M.

R₁₀ and R₁₁ in Formula (C2) or Formula (D2) each independently representan alkyl group, an alkenyl group, an aryl group, a heterocyclic group,an alkoxy group, an aryloxy group, an amino group, an anilino group, ora heterocyclic amino group.

The alkyl group, the alkenyl group, the aryl group, the heterocyclicgroup, the alkoxy group, the aryloxy group, the amino group, the anilinogroup, or the heterocyclic amino group represented by R₁₀ or R₁₁ may befurther substituted with an additional substituent which is any one ofthe substituents represented by R₁ to R₆, and when it is substitutedwith two or more additional substituents, the additional substituentsmay be the same as or different from each other.

R₁₀ and R₁₁ each are preferably independently an alkyl group or an arylgroup from the viewpoints of synthesis suitability and stability of acompound.

When any one of the substituents represented by R₁₀ and R₁₁ is adivalent linking group, the divalent linking group may be a new divalentlinking group formed by binding at least two substituents. For example,the new divalent linking group may be formed by binding at least twodivalent linking groups selected from the group consisting of analkylene group, an aralkylene group, an arylene group, a divalentheterocyclic group, —O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—,—OC(═O)N(Rd)—, —C(═O)N(Re)—, —N(Rd)C(═O)—, —N(Rd)C(═O)O—,—N(Rd)C(═O)N(Re)—, —SO—, —SO₂—, —SO₃—, —SO₂N(Rd)—, —N(Rd)SO₂—,—C(═O)N(Rd)SO₂—, and —SO₂N(Rd)SO₂—.

Rd and Re each independently represent a hydrogen atom, an alkyl group,an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonylgroup, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,or a sulfamoyl group. These alkyl group, aryl group, heterocyclic group,acyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonylgroup, carbamoyl group, and sulfamoyl group may each be substituted withat least one additional substituent which is any one of the substituentsof R₁ to R₆, and when they are substituted with two or more additionalsubstituents, the additional substituents may be the same as ordifferent from each other.

Tautomers of the compounds represented by Formula (1-A2), Formula(1-B2), Formula (C2), and Formula (D2), respectively, will be described.

Tautomers of compounds represented by Formula (1-A2), Formula (1-B2),Formula (C2), and Formula (D2), respectively, may be any tautomer aslong as it is a compound having a structure which may be formed bymovement of one hydrogen atom in the molecule of the compound. Forexample, the tautomers may have structures represented by the followingFormula (a′) to Formula (f′).

In Formulas (a′) to (f′), X₅ is a group which may bind to Ma, and a is 0or 1. Other substituents respectively have the same meanings as inFormula (1-A2), Formula (1-B2), Formula (C2), or Formula (D2).

Next, the preferable ranges and examples of the compounds of theinvention will be described.

It is preferable that Formula (A2) is represented by Formula (1-A2), andFormula (B2) is represented by Formula (1-B2). It is more preferablethat each Formula (A2) is represented by Formula (C2) and Formula (B2)is represented by Formula (D2).

L in Formula (1-A2), Formula (1-B2), Formula (C2), or Formula (D2) ispreferably an alkylene group.

In Formula (A2) or Formula (B2), It is preferable that -(L)-SO₃ ⁻ or-(L)-SO₃M binds to a divalent linking group represented by R₁ or R₆. InFormula (1-A2) or Formula (1-B2), it is preferable that -(L)-SO₃ ⁻ or-(L)-SO₃M binds to a divalent linking group represented by R₈ or R₉. InFormula (C2) or Formula (D2), it is preferable that -(L)-SO₃ ⁻ or-(L)-SO₃M binds to a divalent linking group represented by R₁₀ or R₁₁.

When any one of R₁ to R₆ of Formula (A2) or Formula (B2) is a divalentlinking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M, the divalentlinking group is preferably an alkylene group, an aralkylene group, anarylene group, or a divalent heterocyclic group, or a divalent linkinggroup formed by any one of an alkylene group, an aralkylene group, andan arylene group, and any one of —O—, —S—, —C(═O)O—, —OC(═O)—, —C(═O)—,—OC(═O)N(Rd)—, —C(═O)N(Re)—, —N(Rd)C(═O)—, —N(Rd)C(═O)O—,—N(Rd)C(═O)N(Re)—, —SO—, —SO₂—, —SO₂N(Rd)—, and —N(Rd)SO₂—. Furtherpreferable is an alkylene group, an aralkylene group, or an arylenegroup.

When any one of R₂ to R₅, R₈, and R₉ in Formula (1-A2) or Formula (1-B2)is a divalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M, thedivalent linking group is preferably an alkylene group, an aralkylenegroup, an arylene group, or a divalent heterocyclic group, or a divalentlinking group formed by any one of an alkylene group, an aralkylenegroup, and an arylene group, and any one of —O—, —S—, —C(═O)O—,—OC(═O)—, —C(═O)—, —OC(═O)N(Rd)-, —C(═O)N(Re)-, —N(Rd)C(═O)—,—N(Rd)C(═O)O—, —N(Rd)C(═O)N(Re)-, —SO—, —SO₂—, —SO₂N(Rd)-, and—N(Rd)SO₂—. An alkylene group, an aralkylene group, or an arylene groupis more preferable.

When any one of R₂ to R₅, R₁₀, and R₁₁ in Formula (C2) or Formula (D2)is a divalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M, thedivalent linking group is preferably an alkylene group, an aralkylenegroup, an arylene group, or a divalent heterocyclic group, or a divalentlinking group formed by any one of an alkylene group, an aralkylenegroup, and an arylene group, and any one of —O—, —S—, —C(═O)O—,—OC(═O)—, —C(═O)—, —OC(═O)N(Rd)—, —C(═O)N(Re)—, —N(Rd)C(═O)—,—N(Rd)C(═O)O—, —N(Rd)C(═O)N(Re)—, —SO—, —SO₂—, —SO₂N(Rd)—, and—N(Rd)SO₂—. Further preferable is an alkylene group, an aralkylenegroup, or an arylene group.

The preferable ranges of respective substituents of Formula (A1),Formula (B2), Formula (1-A2), Formula (1-B2), Formula (C2), and Formula(D2) will be described below; however, in a combination of a preferablerange of each substituent with a preferable range of formulae, therespective more preferable ranges are more preferable.

R₁ and R₆ in Formula (A2) or Formula (B2) each are preferablyindependently an alkyl group, an aryl group, a heterocyclic group, agroup represented by —Y₁—C(═X₃)—R₈ or a group represented by—Y₂—C(═X₄)R₉ shown in Formula (1-A2) or Formula (1-B2), or a grouprepresented by —NH—C(═O)—R₁₀ or —NH—C(═O)—R₁₁ shown in Formula (C2) orFormula (D2).

More preferably, R₁ and R₆ are each a group represented by —Y₁—C(═X₃)—R₈or a group represented by —Y₂—C(═X₄)—R₉ shown in Formula (1-A2) orFormula (1-B2), or a group represented by —NH—C(═O)—R₁₀ or —NH—C(═O)—R₁₁shown in Formula (C2) or Formula (D2).

Most preferable is a group represented by —NH—C(═O)—R₁₀ or —NH—C(═O)—R₁₁shown in Formula (C2) and Formula (D2).

R₂ and R₅ in Formula (A2), Formula (B2), Formula (1-A2), Formula (1-B2),Formula (C2), or Formula (D2) each are preferably independently an alkylgroup, an aryl group, a heterocyclic group, an alkoxycarbonyl group, anaryloxycarbonyl group, a cyano group, a carboxyl group, an acyl group, acarbamoyl group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkylsulfonyl group, an arylsulfonyl group, aheterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinylgroup, or a sulfamoyl group; more preferably a perfluoroalkyl group, anaryl group, a heterocyclic group, an alkoxycarbonyl group, anaryloxycarbonyl group, a cyano group, a carboxyl group, an acyl group, acarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, aheterocyclic sulfonyl group, or a sulfamoyl group; further preferably aperfluoroalkyl group, an aryl group, a heterocyclic group, analkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, acarboxyl group, an acyl group, a carbamoyl group, an alkylsulfonylgroup, an arylsulfonyl group, or a sulfamoyl group; and most preferablya perfluoroalkyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a cyano group, a carbamoyl group, an alkylsulfonyl group, or anarylsulfonyl group.

R₃ and R₄ in Formula (A2), Formula (B2), Formula (1-A2), Formula (1-B2),Formula (C2), or Formula (D2) are each preferably independently an alkylgroup, an aryl group, a heterocyclic group, an alkoxycarbonyl group, acyano group, or a carbamoyl group; more preferably an alkyl group, anaryl group, a heterocyclic group, or a cyano group; and most preferablyan alkyl group, an aryl group, or a heterocyclic group.

R₇ in Formula (A2), Formula (B2), Formula (1-A2), Formula (1-B2),Formula (C2), or Formula (D2) is preferably a hydrogen atom, a halogenatom, an alkyl group, an aryl group, or a heterocyclic group; morepreferably a hydrogen atom, an alkyl group, an aryl group, or aheterocyclic group; further preferably a hydrogen atom, an alkyl group,or an aryl group; and most preferably a hydrogen atom.

M in Formula (B2), Formula (1-B2), or Formula (D2) is preferably ahydrogen atom, a trialkylamine having 3 to 14 carbon atoms, a quaternaryammonium having 4 to 20 carbon atoms, a guanidine having 3 to 14 carbonatoms, or an alkali metal, more preferably a trialkylamine having 3 to 9carbon atoms, a quaternary ammonium salt 4 to 8 carbon atoms, or analkali metal, and further preferably an alkali metal.

X₂ in Formula (A2) or Formula (B2) is preferably water, alcohols (e.g.methanol, ethanol, propanol), or a compound described in “Metal Chelate”[1] Takeichi Sakaguchi/Keihei Ueno (1995, Nankodo Co., Ltd.), the same[2] (1996), and the same [3] (1997), and further preferably water oralcohols, and most preferably p is 0.

Ma in Formula (A2), Formula (B2), Formula (1-A2), or Formula (1-B2) ispreferably Fe, Zn, Co, or Cu, further preferably Zn, Co, or Cu, and mostpreferably Zn.

X₁ in Formula (B2), Formula (1-B2), or Formula (D2) is preferably ahalogen atom, a carboxylic acid group, a sulfonic acid group, or aphosphoric acid group, and more preferably a chlorine atom, a carboxylicacid group, or a sulfonic acid group.

R₈ and R₉ in Formula (1-A2) or Formula (1-B2) each are preferablyindependently an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an alkoxy group, an amino group, or an anilinogroup, more preferably an alkyl group, an aryl group, a heterocyclicgroup, an alkoxy group, an amino group, or an anilino group, furtherpreferably an alkyl group, an aryl group, or a heterocyclic group, andmost preferably an alkyl group or an aryl group.

X₃ and X₄ in Formula (1-A2) or Formula (1-B2) each are preferablyindependently NR (in which R represents a hydrogen atom, an alkyl group,an alkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group), a sulfur atom, or anoxygen atom, more preferably —NH—, a sulfur atom, or an oxygen atom, andmost preferably an oxygen atom.

Y₁ and Y₂ in Formula (1-A2) or Formula (1-B2) each are preferablyindependently NR (in which R is a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group), more preferably NR (inwhich R is a hydrogen atom or an alkyl group), and most preferably a—NH— group.

R₁₀ and R₁₁ in Formula (C2) or Formula (D2) each are preferablyindependently an alkyl group, an aryl group, or a heterocyclic group,and more preferably an alkyl group or an aryl group.

Then, examples of the compounds represented by Formula (A2), Formula(B2), Formula (1-A2), Formula (1-B2), Formula (C2), and Formula (D2),respectively, will be shown below, but the invention is not limited tothem.

Compound R₃, R₄ R₈ R₉ A′-1  —CH₃ —CH₃

A′-2  Same as above

Same as above A′-3  Same as above —C₄H₉(t) Same as above A′-4  Same asabove

Same as above A′-5  Same as above

A′-6  Same as above —CH₂OCH₃ Same as above A′-7  Same as above

Same as above A′-8  Same as above —CH₂OCH₂COOC₂H₅ Same as above A′-9 Same as above

Same as above A′-10 Same as above

Same as above A′-11 Same as above

Same as above A′-12 Same as above

Same as above A′-13 Same as above

Same as above A′-14 Same as above —CH₂OCH₂COOH Same as above A′-15 Sameas above

Same as above A′-16 Same as above —CF₃ Same as above A′-17 Same as above—OC₂H₅ —CH₂—S—(CH₂)₂SO₃ ⁻ A′-18 Same as above —NHC₄H₉ Same as aboveA′-19 —C₂H₅ —C₄H₉(t) Same as above

Compound R₃, R₄ R₈ R₉ A′-20

—C₄H₉(t)

A′-21

Same as above

A′-22 —CH₃ Same as above

A′-23 Same as above Same as above —(CH₂)₃S(CH₂)₃SO₃ ⁻ A′-24 Same asabove Same as above

A′-25 Same as above Same as above —(CH₂)₃SO₂(CH₂)₃SO₃ ⁻ A′26 Same asabove Same as above

A′-27 Same as above Same as above

A′-28 Same as above Same as above

A′-29 Same as above Same as above

A′-30 Same as above

A′-31 Same as above

A′-32 Same as above

Same as above A′-33 Same as above Same as above

A′-34 Same as above

Same as above

Compound R₃, R₄ R₈ R₉ A′-35 —CH₃

A′-36 Same as above

Same as above A′-37 Same as above

Same as above A′-38 Same as above

Same as above A′-39 Same as above

Same as above A′-40 Same as above

Same as above A′-41 Same as above

Same as above A′-42 Same as above

A′-43 Same as above —C₄H₉(t)

Compound R₃, R₄ R₈ R₉ B′-1 

—C₄H₉(t)

B′-2 

Same as above Same as above B′-3 

Same as above Same as above B′-4 

Same as above Same as above B′-5 

Same as above B′-6 

Same as above B′-7  Same as above

Same as above B′-8 

—C₄H₉(t) Same as above B′-9  —C₄H₉(t) Same as above Same as above B′-10—CH₃

Same as above B′-11

Same as above B′-12 Same as above —(CH₂)₃S(CH₂)₃SO₃Na —(CH₂)₃S(CH₂)₃SO₃⁻ B′-13 Same as above

B′-14 —CH₃ Same as above Same as above B′-15

—(CH₂)₃S(CH₂)₃SO₃Na —(CH₂)₃S(CH₂)₃SO₃ ⁻ B′-16

Compound R₃ R₄ R₈ R₉ C′-1 

—CH₃ —C₄H₉(t)

C′-2 

Same as above Same as above Same as above C′-3 

Same as above Same as above C′-4  Same as above Same as above

Same as above C′-5 

Same as above C′-6 

Same as above C′-7  Same as above Same as above

Same as above C′-8  Same as above Same as above

Same as above C′-9  Same as above Same as above

Same as above C′-10 Same as above Same as above

Same as above C′-11 Same as above Same as above

C′-12 Same as above Same as above —(CH₂)₃S(CH₂)₃SO₃Na —(CH₂)₃S(CH₂)₃SO₃⁻ C′-13 —CH₃ —CH₃

C′-14

—CH₂OCH₃ Same as above Same as above C′-15

—(CH₂)₃S—C₈H₁₇ Same as above Same as above

Compound R₃ R₄ R₈ R₉ D′-1 

—C₄H₉(t)

D′-2  Same as Same as —CH₂(CH₂)₇CH═CH₂ Same as above above above D′-3 Same as Same as —CH₂(CH₂)₅CH₂CH═CHCH₂C₅H₁₁ Same as above above aboveD′-4  Same as above Same as above

Same as above D′-5  Same as Same as —CH₂OCH₂COOH Same as above aboveabove D′-6  Same as above Same as above

Same as above D′-7  Same as above Same as above

Same as above D′-8  Same as above Same as above

Same as above D′-9  Same as above Same as above

Same as above D′-10

Same as above D′-11 Same as above Same as above

Same as above D′-12 Same as above Same as above

Same as above D′-13 Same as above Same as above

D′-14 —CH₃ —CH₃ Same as above Same as above

Compound R₂ R₃ R₄ R₅ R₈ E′-1 

—CH₃  CH₃ —SO₂CH₃ —C₄H₉(t) E′-2  Same as above Same as above Same asabove

Same as above E′-3  Same as above

Same as above Same as above E′-4  Same as above —CH₃ —CH₃ Same as above

E′-5  —SO₂CH₃ Same as above Same as above

Same as above E′-6  Same as Same as Same as above Same as above —C₄H₉(t)above above E′-7  —SO₂C₄H₉ —CH₃ —CH₃ Same as above Same as above E′-8 

Same as above Same as above Same as above Same as above E′-9 

Same as above Same as above E′-10

Same as above Same as above Same as above Same as above E′-11 —COOC₂H₅Same as Same as above Same as above Same as above above E′-12

Same as above Same as above Same as above Same as above E′-13

Same as above Same as above

Same as above E′-14 Same as —CH₃ —CH₃ Same as above Same as above aboveE′-15 —COOC₂H₅

—COOC₂H₅ Same as above

The compounds represented by Formula (A2), Formula (B2), Formula (C2),and Formula (D2), respectively, may each be synthesized by the methoddescribed in US Application Publication No. 2008/0076044 A1.

The amount of at least one compound selected from the compounds ofFormula (A2) and Formula (B2), which is included in the colored curablecomposition of the second exemplary embodiment of the invention, variesdepending on a molecular weight and a molar absorption coefficientthereof, and is preferably from 0.5 to 80% by mass, more preferably from0.5 to 60% by mass, and most preferably from 0.5 to 50% by mass, withrespect to the total solid contents of the colored curable composition.

The colored curable composition according to the second exemplaryembodiment of the invention and the color filter using the coloredcurable composition may include a phthalocyanine compound such as thosedisclosed in US Application Publication No. 2008/0076044 A1, atriarylmethane coloring agent having an absorption maximum at 550 to 650nm such as C.I. Acid Blue 7, C.I. Acid Blue 83, C.I. Acid Blue 90, C.I.Solvent Blue 38, C.I. Acid Violet 17, C.I. Acid Violet 49 or C.I. AcidGreen 3, in addition to the compounds of Formula (A2), Formula (B2),Formula (C2), and Formula (D2) and tautomers thereof.

Further, a xanthene colorant having an absorption maximum at 500 nm to600 nm, for example, C. I. Acid. Red 289 may also be used.

The phthalocyanine coloring agent or the triarylmethane coloring agentmay be used as long as the effect of the invention is not deteriorated,and the amount thereof is preferably from 0.5 to 50% by mass withrespect to the total solid contents of the colored curable compositionof the invention.

In order to manufacture a blue filter array, it is preferable that amixture of a metal complex of the invention and at least one of thephthalocyanine coloring agents is used.

In this case, a proportion of them within the mixture varies dependingon their molar absorption coefficients, spectrometric propertiesrequired, film thickness, and the like. Generally, the proportion (i.e.,total amount of metal complex of the invention: phthalocyanine coloringagent) is from 10:1 to 1:20, and preferably in a range of from 5:1 to1:10.

Binder

It is preferable that the colored curable composition according to thefirst or second exemplary embodiment of the invention includes at leastone binder. The binder used in the invention is not particularly limitedas long as it is alkali-soluble, and is preferably selected from theviewpoints of heat resistance, developability, availability, and thelike.

The alkali-soluble binder is preferably a linear organic polymer solublein organic solvents and developable with an aqueous weakly alkalinesolution. Examples of such linear organic polymer include polymershaving a carboxylic acid at their side chain, for example methacrylicacid copolymers, acrylic acid copolymers, itaconic acid copolymers,crotonic acid copolymers, maleic acid copolymers andpartially-esterified maleic acid copolymers as those described in thespecifications of JP-A No. 59-44615 and JP-B Nos. 54-34327, 58-12577 and54-25957. Acidic cellulose derivatives having a carboxylic acid at theside chain are particularly useful.

Other useful binders include polymers prepared by adding an acidanhydride to a polymer having a hydroxyl group, polyhydroxystyreneresins, polysiloxane resins, poly(2-hydroxyethyl (meth)acrylate),polyvinyl pyrrolidone, polyethylene oxide and polyvinyl alcohol.

Alternatively, the binder used in the invention may be a copolymer ofmonomers having a hydrophilic group, and examples of the monomersinclude alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate,glycerol (meth)acrylate, (meth)acrylamide, N-methylolacrylamide,secondary and tertiary alkylacrylamide, dialkylaminoalkyl(meth)acrylate, morpholino (meth)acrylate, N-vinylpyrrolidone,N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl(meth)acrylate, ethyl (meth)acrylate, branched or straight propyl(meth)acrylate, branched or straight butyl (meth)acrylate, andphenoxyhydroxypropyl (meth)acrylate.

As other monomers having a hydrophilic group, monomers containing atetrahydrofurfuryl group, a phosphoric acid moiety, a phosphoric acidester moiety, a quaternary ammonium salt moiety, an ethyleneoxy chain, apropyleneoxy chain, a sulfonic acid moiety and a salt thereof, or amorpholinoethyl group are also useful.

Alternatively, in order to improve the crosslinking efficacy, the bindermay have a polymerizable group in a side chain thereof. For example,polymers containing an allyl group, a (meth)acryl group, anallyloxyalkyl group or the like are also useful.

Examples of the polymers having a polymerizable group include KSResist-106 (trade name, manufactured by Osaka Organic Chemical IndustryLtd.), and CYCLOMER P series (registered name, manufactured by DICELChemical Industries, Ltd.).

Moreover, in order to increase the strength of a cured film, analcohol-soluble nylon or polyether of 2,2-bis(4-hydroxyphenyl)-propaneand epichlorohydrin is also useful.

Among the various binders, from a viewpoint of heat resistance, thebinder to be used in the invention is preferably a polyhydroxystyreneresin, a polysiloxane resin, an acryl resin, an acrylamide resin, or anacryl/acrylamide copolymer resin. Alternatively, from a viewpoint ofdevelopability control, the binder to be used in the invention ispreferably an acryl resin, an acrylamide resin, or an acryl/acrylamidecopolymer resin.

Examples of the acryl resin preferably include a copolymer including amonomer selected from benzyl (meth)acrylate, (meth)acryl, hydroxyethyl(meth)acrylate, and (meth)acrylamide, KS-RESIST-106 (trade name,manufactured by Osaka Organic Chemical Industry Ltd.), and CYCLOMERP-series.

As the binder used in the invention, an alkali-soluble phenol resin mayalso be used. The alkali-soluble phenol resin may be preferably usedwhen the composition of the invention is used as a positive-workingcomposition. Examples of the alkali-soluble phenol resin include novolakresins and vinyl polymers.

Examples of the novolak resins include a product obtained bycondensation of a phenol and an aldehyde in the presence of an acidcatalyst. Examples of the phenol include phenol, cresol, ethylphenol,butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol,naphthol, and bisphenol A.

Examples of the aldehyde include formaldehyde, paraformaldehyde,acetaldehyde, propionaldehyde, and benzaldehyde.

As the phenol, only one phenol compound, or alternatively a combinationof two or more phenol compounds, may be used. As the aldehyde, only onealdehyde compound may be used, or alternatively a combination of two ormore aldehyde compounds may be used.

Specific examples of the novolak resin include metacresol, paracresol,and condensation products of a mixture thereof with formalin.

The molecular weight distribution of the novolak resin may be regulatedby fractionation or the like. Alternatively, a low-molecular weightcomponent having a phenolic hydroxy group such as bisphenol C orbisphenol A may be mixed with the novolak resin.

The binder is preferably a polymer having a mass average molecularweight (in terms of polystyrene measured by GPC method) of from 1,000 to2×10⁵, further preferably from 2,000 to 1×10⁵, and particularlypreferably from 5,000 to 5×10⁴.

The amount of the binder in the colored curable composition ispreferably 10% by mass to 90% by mass, further preferably 20% by mass to80% by mass, particularly preferably 30% by mass to 70% by mass, withrespect to the total solid contents of the colored curable compositionof the invention.

Crosslinking Agent

The colored curable composition according to the first exemplaryembodiment of the invention includes, as a coloring agent, at least oneselected from the group consisting of a compound of Formula (A1) and acompound of Formula (B1), and tautomers thereof. The colored curablecomposition according to the second exemplary embodiment of theinvention includes, as a coloring agent, at least one selected from thegroup consisting of a compound of Formula (A2) and a compound of Formula(B2), and tautomers thereof. For this reason, the colored curablecompositions of the first and second exemplary embodiments of theinvention have excellent color purity, have a high adsorptioncoefficient even when the compositions are formed into a thin film, andhave excellent fastness, as compared with the previous ones. When thecompositions each further include the crosslinking agent, a highly curedfilm is obtained.

Any crosslinking agent may be used without particular limitation insofaras it can cure a film through a crosslinking reaction. Examples of thecrosslinking agent include (a) an epoxy resin, (b) a melamine compound,guanamine compound, glycoluril compound, or urea compound substituted byat least one substituent selected from a methylol group, an alkoxymethylgroup, and an acyloxymethyl group, and (c) a phenol compound, naphtholcompound, or hydroxyanthracene compound substituted by at least onesubstituent selected from a methylol group, an alkoxymethyl group, andan acyloxymethyl group. Among the above, polyfunctional epoxy resins areparticularly preferable.

As (a) the epoxy resin, any epoxy resin may be used as long as it has anepoxy group and crosslinking property. Examples thereof include divalentglycidyl group-containing low-molecular weight compounds such asbisphenol A glycidyl ether, ethylene glycol diglycidyl ether, butanedioldiglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyldiglycidyl ether, phthalic acid diglycidyl ester, orN,N-diglycidylaniline; trivalent glycidyl group-containing low-molecularweight compounds such as trimethylolpropane triglycidyl ether,trimethylolphenol triglycidyl ether, or TRIS P-PA triglycidyl ether;tetravalent glycidyl group-containing low-molecular weight compoundssuch as pentaerythritol tetraglycidyl ether or tetramethylol bisphenol Atetraglycidyl ether; polyvalent glycidyl group-containing low-molecularweight compounds such as dipentaerythritol pentaglycidyl ether ordipentaerythritol hexaglycidyl ether; glycidyl group-containinghigh-molecular weight compounds such as polyglycidyl (meth)acrylate or a1,2-epoxy-4-(2-oxylanyl)cyclohexane adduct of2,2-bis(hydroxymethyl)-1-butanol.

The number of substitution with the methylol group, the alkoxymethylgroup, and/or the acyloxymethyl group included in the crosslinking agent(b) is 2 to 6 in the case of the melamine compound, and 2 to 4 in thecase of the glycoluril compound, the guanamine compound, or the ureacompound, preferably 5 to 6 in the case of the melamine compound, and 3to 4 in the case of the glycoluril compound, the guanamine compound, orthe urea compound.

The melamine compound, the guanamine compound, the glycoluril compoundand the urea compound of (b) are collectively referred to as“compound(s) (b)” (or a methylol group-containing compound, alkoxymethylgroup-containing compound, or acyloxymethyl group-containing compound)in some cases hereinafter.

The methylol group-containing compound of the compound (b) may beobtained by heating the alkoxymethyl group-containing compound of thecompound (b) in an alcohol in the presence of an acid catalyst such ashydrochloric acid, sulfuric acid, nitric acid, or methanesulfonic acid.The acyloxymethyl group-containing compound of the compound (b) may beobtained by mixing and stirring the methylol group-containing compoundof the compound (b) with acyl chloride in the presence of a basiccatalyst.

Hereinafter, specific examples of the compound (b) having any of thesubstituents are described.

Examples of the melamine compound include a hexamethylol melamine,hexamethoxymethyl melamine, compounds in which 1 to 5 methylol groups ofhexamethylol melamine are methoxymethylated or mixtures thereof,hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and compounds inwhich 1 to 5 methylol groups of hexamethylol melamine areacyloxymethylated or mixtures thereof.

Examples of the guanamine compound include tetramethylol guanamine,tetramethoxymethyl guanamine, compounds in which 1 to 3 methylol groupsof tetramethylol guanamine are methoxymethylated or mixtures thereof,tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, and compoundsin which 1 to 3 methylol groups of tetramethylol guanamine areacyloxymethylated or mixtures thereof.

Examples of the glycoluril compound include tetramethylol glycoluril,tetramethoxymethyl glycoluril, compounds in which 1 to 3 methylol groupsof tetramethylol glycoluril are methoxymethylated or mixtures thereof,and compounds in which 1 to 3 methylol groups of tetramethylolglycoluril are acyloxymethylated or mixtures thereof.

Examples of the urea compound include tetramethylolurea,tetramethoxymethylurea, compounds in which 1 to 3 methylol groups oftetramethylolurea are methoxymethylated or mixtures thereof, andtetramethoxyethylurea.

The compounds (b) may be used singly, or may be used in combination oftwo or more of them.

The crosslinking agent (c), that is, a phenol compound, naphtholcompound, or hydroxyanthracene compound substituted with at least onegroup selected from a methylol group, an alkoxymethyl group, and anacyloxymethyl group suppresses intermixing with an overcoat photoresist,and further enhances a film strength by thermal crosslinking like thecase of the crosslinking agent (b).

These compounds are collectively referred to as “compound(s) (c)” (or amethylol group-containing compound, an alkoxymethyl group-containingcompound, or an acyloxymethyl group-containing compound) in some caseshereinafter.

The total number of methylol groups, acyloxymethyl groups, oralkoxymethyl groups included in the crosslinking agent (c) has to be atleast 2 per molecule. For example, a compound in which a phenolcompound, serving as a skeleton, is substituted at all of 2-positionsand 4-positions is preferable from the viewpoints of thermalcrosslinking properties and storage stability. When the skeleton is anaphthol compound or a hydroxyanthracene compound, all of ortho- andpara-positions relative to the OH group in the compound is preferablysubstituted. The 3- or 5-position of the phenol compound as the skeletonmay be unsubstituted or may have a substituent. Also in the naphtholcompound as the skeleton, positions other than the ortho-positionrelative to the OH group may be unsubstituted or may have a substituent.

The methylol group-containing compound of the compound (c) may beobtained by using, as a raw material, a compound in which anortho-position or a para-position (2-position or 4-position) of aphenolic OH group is a hydrogen atom, and subjecting this compound to areaction with formalin in the presence of a basic catalyst such assodium hydroxide, potassium hydroxide, ammonia, or tetraalkylammoniumhydroxide.

The alkoxymethyl group-containing compound of the compound (c) may beobtained by heating the methylol group-containing compound of thecompound (c) in an alcohol in the presence of an acid catalyst such ashydrochloric acid, sulfuric acid, nitric acid, or methanesulfonic acid.

The acyloxymethyl group-containing compound of the compound (c) may beobtained by subjecting the methylol group-containing compound of thecompound (c) to a reaction with acyl chloride in the presence of a basiccatalyst.

Examples of a skeleton compound in the crosslinking agent (c) include aphenol compound, a naphthol compound, and a hydroxyanthracene compoundin each of which an ortho-position or a para-position of a phenolic OHgroup is unsubstituted. Examples thereof include respective isomers ofphenol and cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol,bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TRIS P-PA(trade name, manufactured by Honsyu Chemical Industry Co Ltd.),naphthol, dihydroxynaphthalene, and 2,7-dihydroxyanthracene.

Specific examples of the crosslinking agent (c) includetrimethylolphenol, tri(methoxymethyl)phenol, a compound in which 1 to 2methylol groups of trimethylolphenol are methoxymethylated,trimethylol-3-cresol, tri(methoxymethyl)-3-cresol, a compound in which 1to 2 methylol groups of trimethylol-3-cresol are methoxymethylated,dimethylolcresols such as 2,6-dimethylol-4-cresol,tetramethylolbisphenol A, tetramethoxymethylbisphenol A, a compound inwhich 1 to 3 methylol groups of tetramethylolbisphenol A aremethoxymethylated, tetramethylol-4,4′-bishydroxybiphenyl,tetramethoxymethyl-4,4′-bishydroxybiphenyl, a hexamethylol of TRIS P-PA,a hexamethoxymethyl of TRIS P-PA, a compound in which 1 to 5 methylolgroups of a hexamethylol of TRIS P-PA are methoxymethylated, andbishydroxymethylnaphthalene diol.

Examples of the hydroxyanthracene compound include1,6-dihydroxymethyl-2,7-dihydroxyanthracene.

Examples of the acyloxymethyl group-containing compound include acompound in which a part or all of methylol groups of the methylolgroup-containing compound are acyloxymethylated.

Among these compounds, examples of a preferable compound includetrimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A,a hexamethylol of TRIS P-PA (manufactured by Honsyu Chemical Industry CoLtd.), and a phenol compound in which methylol groups of them aresubstituted with an alkoxymethyl group, or both of methylol group and analkoxymethyl group.

These compounds (c) may be used singly, or may be used in combination oftwo or more of them.

When a crosslinking agent is included, the total amount of thecrosslinking agents (a) to (c) in the coloring agent-containing curablecomposition varies depending on a material, and is preferably 1 to 70%by mass, more preferably 5 to 50% by mass, particularly preferably 7 to30% by mass, with respect to the total solid content (mass) of thecomposition. When the total amount is in this range, sufficient curingdegree and dissolution property of an unexposed area may be retained,and deficiency of a curing degree at an exposed area, and remarkablereduction in dissolution property of an unexposed area may be prevented.

Polymerizable Monomer

It is preferable that the colored curable composition according to thefirst or second exemplary embodiment of the invention includes at leastone polymerizable monomer. The colored curable composition includes apolymerizable monomer mainly when the colored curable composition isformed into a negative-working composition.

The polymerizable monomer together with a photopolymerization initiatordescribed later may be included in a positive-working compositioncontaining a naphthoquinonediazide compound described later, and, inthis case, a curing degree of a formed pattern may be more increased.The polymerizable monomer will be described hereinbelow.

The polymerizable monomer is preferably a compound having a boilingpoint of 100° C. or higher under a normal pressure and having at leastone addition-polymerizable ethylenic unsaturated group. Examples thereofinclude monofunctional acrylates and methacrylates such as polyethyleneglycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, andphenoxyethyl (meth)acrylate; polyfunctional acrylates and(meth)acrylates such as polyethylene glycol di(meth)acrylate,trimethylolethane tri(meth)acrylate, neopentylglycol di(meth)acrylate,pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropanetri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate;compounds obtained by adding ethylene oxide or propylene oxide to apolyfunctional alcohol such as glycerin or trimethylol and(meth)acrylating this product; urethane acrylates such as thosedescribed in JP-B Nos. 48-41708, 50-6034, and JP-A No. 51-37193; andpolyester acrylates and epoxy acrylates, which are reaction products ofan epoxy resin and (meth)acrylic acid, described in JP-A No. 48-64183and JP-B Nos. 49-43191 and 52-30490, and mixtures thereof.

Further, those disclosed as a photocurable monomer or oligomer inJournal of the Adhesion Society of Japan, Vol. 20, No. 7, pp. 300 to 308is also used as the polymerizable monomer.

The amount of the polymerizable monomer in the colored curablecomposition is preferably 0.1% by mass to 90% by mass, furtherpreferably 1.0% by mass to 80% by mass, particularly preferably 2.0% bymass to 70% by mass, with respect to the solid contents in the coloredcurable composition.

Radiation-Sensitive Compound

The colored curable composition according to the first or secondexemplary embodiment of the invention includes at least oneradiation-sensitive compound. The radiation-sensitive compound is ableto effect chemical reactions such as generation of radicals, acids andbases in response to irradiation of UV light of which wavelength is 400nm or less. The radiation-sensitive compound is used for making thealkali-soluble binder insoluble by cross-linking, polymerization,decomposition of acidic groups, or the like, or for making coatinglayers insoluble to an alkali developer by inducing polymerization ofthe polymerizable monomer and oligomer remaining in the coating layer orcross-linking of the cross-linking agent.

In particular, when the colored curable composition according to thefirst or second exemplary embodiment of the invention is composed in anegative-working composition, it is preferable that the colored curablecomposition includes a photopolymerization initiator. When thephotosensitive colored curable composition is composed in apositive-working composition, it is preferred that the colored curablecomposition includes a naphthoquinonediazide compound.

Photopolymerization Initiator

Next, a photopolymerization initiator included in the colored curablecomposition of the first or second exemplary embodiment of the inventionwhen the colored curable composition is a negative-working compositionwill be described.

The photopolymerization initiator is not particularly limited as long asit can polymerize the polymerizable monomer, and it is preferable thatthe initiator is selected from the viewpoints of properties, aninitiation efficiency, an absorption wavelength, availability, and thecost.

The positive-working composition containing a naphthoquinonediazidecompound may further include the photopolymerization initiator. In thiscase, a curing degree of a formed pattern may be more increased.

Examples of the photopolymerization initiator include at least oneactive halogen compound selected from a halomethyloxadiazole compoundand a halomethyl-s-triazide compound, a 3-aryl-substituted coumarincompound, a lophine dimer, a benzophenone compound, an acetophenonecompound and a derivative thereof, a cyclopentadiene-benzene-ironcomplex and a salt thereof, and an oxime compound.

Examples of the active halogen compound such as halomethyloxadiazoleinclude 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described inJP-B No. 57-6096, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole,2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole.

Examples of the halomethyl-s-triazine compound include avinyl-halomethyl-s-triazine compound described in JP-B No. 59-1281, and2-(naphtho-1-yl)-4,6-bis(halomethyl)-s-triazine compound and a4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazine compound described inJP-A No. 53-133428.

Other examples of the photopolymerizable initiator include2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine,2,6-bis(trichloromethyl)-4-(3,4-methylenedioxyphenyl)-1,3,5-triazine,2,6-bis(trichloromethyl)-4-(4-methoxyphenyl)-1,3,5-triazine,2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine,2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine,2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-ethoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-butoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-[4-(2-methoxyethyl)-naphtho-1-yl]-4,6-bis(trichloromethyl)-s-triazine,

2-[4-(2-ethoxyethyl)-naphtho-1-yl]-4,6-bis(trichloromethyl)-s-triazine,2-[4-(2-butoxyethyl)-naphtho-1-yl]-4,6-bis(trichloromethyl)-s-triazine,2-(2-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(6-methoxy-5-methyl-naphtho-2-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(6-methoxy-naphtho-2-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(5-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4,7-dimethoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(6-ethoxy-naphtho-2-yl)-4,6-bis(trichloromethyl)-s-triazine,2-(4,5-dimethoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine,4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2-6-bis(trichloromethyl)-s-triazine,4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-methyl-p-N,N-di(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-[p-N,N-di(phenyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[m-bromo-p-N,N-di(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,

4-[m-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine,4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine,and4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine.

In addition, TAZ Series such as TAZ-107, TAZ-110, TAZ-104, TAZ-109,TAZ-140, TAZ-204, TAZ-113 and TAZ-123 (all trade names, manufactured byMidori Kagaku Co., Ltd.), T Series such as T-OMS, T-BMP, T-R, and T-B(all trade names, manufactured by PANCHIM, Irgacure Series), IRGACURESeries such as IRGACURE 369, IRGACURE 784, IRGACURE 651, IRGACURE 184,IRGACURE 500, IRGACURE 1000, IRGACURE 149, IRGACURE 819, and IRGACURE261, Darocure Series such as DAROCURE 1173 (all registered names,manufactured by Ciba-Geigy), 4,4′-bis(diethylamino)-benzophenone,2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione,1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,2-benzyl-2-dimethylamino-4-morpholinobutyrophenone,2,2-dimethoxy-2-phenylacetophenone,2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer,2-(o-fluorophenyl)-4,5-diphenylimidazolyl dimer,2-(o-methoxyphenyl)-4,5-diphenylimidazolyl dimer,2-(p-methoxyphenyl)-4,5-diphenylimidazolyl dimer,2-(p-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer,2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer,2-(p-methylmercaptophenyl)-4,5-diphenylimidazolyl dimer, and benzoinisopropyl ether are usefully used.

Particularly preferable examples include oxime-O-acyl compounds such as2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carboazol-3-yl]ethanone.

In the photosensitive colored curable composition of the first or secondexemplary embodiment of the invention, any of other knownphotopolymerization initiators may be used in combination with theaforementioned photopolymerization initiator.

Specifically, examples of the other known photopolymerization initiatorsinclude a vicinal polyketolaldonyl compound such as those disclosed inU.S. Pat. No. 2,367,660, an α-carbonyl compound such as those disclosedin U.S. Pat. Nos. 2,367,661 and 2,367,670, an acyloin ether such asthose disclosed in U.S. Pat. No. 2,448,828, an aromatic acyloin compoundsubstituted with a-hydrocarbon such as those disclosed in U.S. Pat. No.2,722,512, a polynuclear quinone compound such as those disclosed inU.S. Pat. Nos. 3,046,127 and 2,951,758, a combination oftriallylimidazole dimer/p-aminophenyl ketone such as those disclosed inU.S. Pat. No. 3,549,367, and benzothiazolecompound/trihalomethyl-s-triazine compound such as those disclosed inJP-B No. 51-48516.

The amount of the photopolymerization initiator in the colored curablecomposition according to the first or second exemplary embodiment of theinvention is preferably 0.01 to 50% by mass, more preferably 1 to 30% bymass, particularly preferably 1 to 20% by mass, with respect to thesolid content of the polymerizable monomer. When the amount is in thisrange, polymerization proceeds good, and an excellent film strength isobtained.

A sensitizer and/or a light stabilizer may be used together with thephotopolymerization initiator.

Examples thereof include benzoin, benzoin methyl ether, 9-fluorenone,2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone,2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone,2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone,2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone,2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone,2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzil,dibenzalacetone, p-(dimethylamino)phenyl styryl ketone,p-(dimethylamino)phenyl-p-methyl styryl ketone, benzophenone,p-(dimethylamino)benzophenone (or Michler's ketone),p-(diethylamino)benzophenone, benzoanthrone, a benzothiazole compoundsuch as those described in JP-B No. 51-48516, Tinuvin 1130, and Tinuvin400.

Besides, it is preferable to further add a thermal polymerizationinhibitor such as hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol,pyrogallol, t-butylcatechol, benzoquinone,4,4′-thiobis(3-methyl-6-t-butylphenol),2,2′-methylenebis(4-methyl-6-t-butylphenol), or 2-mercaptobenzimidazole.

Naphthoquinonediazide Compound

Next, a naphthoquinonediazide compound included in the colored curablecomposition according to the first or second exemplary embodiment of theinvention when the curable composition is formed into a positive-workingcomposition will be described.

The naphthoquinonediazide compound refers to a compound containing atleast one o-quinonediazide group. Examples thereof includeo-naphthoquinonediazide-5-sulfonic acid ester,o-naphthoquinonediazide-5-sulfonic acid amide,o-naphthoquinonediazide-4-sulfonic acid ester, ando-naphthoquinonediazide-4-sulfonic acid amide. These esters and amidecompounds may be produced by known methods using, for example, a phenolcompound represented by Formula (1) described in JP-A Nos. 2-84650 and3-49437.

When the colored curable composition of the first or second exemplaryembodiment of the invention is formed into a positive-workingcomposition, it is preferable that the alkali-soluble phenol resin andthe crosslinking agent are usually dissolved in an organic solvent atproportions of about 2 to 50% by mass and about 2 to 30% by mass,respectively. In the case of the colored curable composition of thefirst exemplary embodiment, the amount of the naphthoquinonediazidecompound is preferably about 2% by mass to 30% by mass, and the amountof one or more compounds (colorants) selected from Formula (A1) andFormula (B1) is preferably about 2% by mass to 50% by mass, with respectto a solution in which the binder and the crosslinking agent aredissolved. In the case of the colored curable composition of the secondexemplary embodiment, the amount of the naphthoquinonediazide compoundis preferably about 2% by mass to 30% by mass, and the amount of one ormore compounds (colorants) selected from Formula (A2) and Formula (B2)is preferably about 2% by mass to 50% by mass, with respect to asolution in which the binder and the crosslinking agent are dissolved.

Solvent

Upon preparation of the colored curable composition of the first orsecond exemplary embodiment of the invention, generally, a solvent maybe used. The solvent to be used is not basically particularly limited aslong as it satisfies solubility of respective components of thecomposition, and coating property of the photosensitive colored curablecomposition of the first or second exemplary embodiment, and the solventis preferably selected in view of solubility, coating property, andsafety of the binder.

Examples of the solvent include esters, for example, ethyl acetate,n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate,isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate,butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyloxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate,ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethylethoxyacetate, 3-oxypropionic acid alkyl esters such as methyl3-oxypropionate and ethyl 3-oxypropionate (e.g. methyl3-methoxypropionate, ethyl 3-methoxypropionate, methyl3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid alkylesters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl2-oxypropionate (e.g. methyl 2-methoxypropionate, ethyl2-methoxypropionate, propyl 2-methoxypropionate, methyl2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methylpyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethylacetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate; ethers,for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether,methylcellosolve acetate, ethylcellosolve acetate, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, propylene glycol methyl ether, propylene glycol methylether acetate, propylene glycol ethyl ether acetate, and propyleneglycol propyl ether acetate; ketones, for example, methyl ether ketone,cyclohexanone, and 2-heptanone, and 3-heptanone; and aromatichydrocarbons, for example, toluene and xylene.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethylether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone,cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propyleneglycol methyl ether, and prolylene glycol methyl ether acetate are morepreferable.

Additives

If necessary, the colored curable composition of the first or secondexemplary embodiment of the invention may further include any of variousadditives, for example, fillers, polymer compounds other than theaforementioned polymer compounds, surfactants, adhesion promoters,antioxidants, ultraviolet absorbing agents, and aggregation inhibitors.

Specific examples of the various additives include fillers such as glassor alumina; polymer compounds other than binder resins, such aspolyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkylether, and polyfluoroalkyl acrylate; nonionic surfactants, cationicsurfactants, or anionic surfactants; adhesion promoters such asvinyltrimethoxysilane, vinyltriethoxysilane,vinyltris(2-methoxyethoxy)silane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropylmethyldimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane, and3-mercaptopropyltrimethoxysilane; antioxidants such as2,2-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;ultraviolet absorbing agents such as2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole andalkoxybenzophenone; and aggregation inhibitors such as sodiumpolyacrylate.

Alternatively, when alkali dissolution property of a region to bedevelopment-removed (for example, in the case of a negative-workingcomposition, an uncured area), and developability of the photosensitivecolored curable composition of the first or second exemplary embodimentof the invention is intended to be further improved, an organiccarboxylic acid, preferably a low-molecular weight organic carboxylicacid having a molecular weight of 1,000 or less may be added to thecomposition. Examples thereof include aliphatic monocarboxylic acidssuch as formic acid, acetic acid, propionic acid, butyric acid, valericacid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, andcaprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, brassilic acid, methylmalonic acid,ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid,tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylicacids such as tricarballilic acid, aconitic acid, and camphoronic acid;aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminicacid, hemellitic acid, and mesitylene acid; aromatic polycarboxylicacids such as phthalic acid, isophthalic acid, terephthalic acid,trimellitic acid, trimesic acid, mellophanic acid, and pyromelliticacid; and other carboxylic acids such as phenylacetic acid, hydratropicacid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropicacid, cinnamic acid, methyl cinnamate, benzyl cinnamate,cinnamilydeneacetic acid, coumaric acid, and umbellic acid.

The colored curable composition of the first or second exemplaryembodiment of the invention may be suitably used for forming a coloringpixel of a color filter used in a liquid crystal display device (LCD) ora solid-state imaging device (e.g. CCD, CMOS etc.), or for producing aprinting ink, an ink jet ink, or a paint. Particularly, the compositionmay be suitably used for forming a coloring pixel for a solid-stateimaging device such as CCD and CMOS.

The colored curable composition of the invention is preferably used forforming a coloring pattern which is fine and thin, and is particularlysuitable for forming a color filter for a solid-state imaging devicerequiring a good rectangular cross-section profile. Specifically, whenthe size of a pixel pattern (side length of a pixel pattern seen from asubstrate normal line direction) constituting the color filter is 2 μmor less (e.g. 0.5 to 2.0 μm), since the coloring agent amount isincreased and further, the hue is a blue system, line width sensitivityis deteriorated, and the DOF margin becomes narrow and, as a result,pattern forming properties are easily impaired. This becomesparticularly pronounced when the size of the pixel pattern is 1.0 to 1.7μm (or, further, 1.2 to 1.5 μm). On the other hand, in the case of athin film having a thickness of 1 μm or less, the amount of componentsother than the coloring agent in the film contributing tophotolithography properties is relatively decreased, and increase in thecoloring agent amount further decreases the amount of other components,whereby sensitivity is reduced and, at a low light exposure amountregion, a pattern is easily peeled off. In such a case, thermal saggingis easily caused by thermal treatment such as post-baking. These defectsare particularly pronounced when the film thickness is 0.005 μm to 0.9μm (or, further, 0.1 μm to 0.7 μm).

Color Filter and Method of Producing the Same

The color filter of the first or second exemplary embodiment of theinvention will be described in detail through a method of producing thesame.

In the method of producing the color filter of the first or secondexemplary embodiment of the invention, the colored curable compositionof the first or second exemplary embodiment of the invention is used.The color filter of the first or second exemplary embodiment of theinvention has a negative-working or positive-working colored pattern(resist pattern) image formed in such a manner that the colored curablecomposition of the first or second exemplary embodiment of the inventionis applied on a support by a coating method such as rotation coating,casting coating or roll coating to form a radiation-sensitivecomposition layer, and the layer is irradiated with light via apredetermined mask pattern, followed by development using a developer.

A light source for light exposure, which may be applied to the coloredcurable composition of the first or second exemplary embodiment of theinvention is not particularly limited, but may be a light source havinga wavelength of 400 nm or less. For example, lamp light sources such asa xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercurylamp, a ultrahigh pressure mercury lamp, a metal halide lamp, a mediumpressure mercury lamp, a low pressure mercury lamp, a carbon arc, and afluorescent lamp, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), a Krion laser (356 nm, 351 nm, 10 mW to 1 W), a solid laser such as acombination of Nd:YAG (YVO4) and SHG crystal×two times (355 nm, 5 mW to1 W), a combination of a waveguide wavelength conversion element andAlGaAs, or a waveguide wavelength conversion element and an AlGaInP orAlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), or a pulselaser such as a N2 laser (337 nm, pulse 0.1 to 10 mJ) or XeF (351 nm,pulse 10 to 250 mJ) may be utilized. When only a specified wavelength isused, an optical filter may be utilized.

Further, ultraviolet rays such as an ArF excimer laser (wavelength 193nm), a KrF excimer laser (wavelength 248 nm), and an i-ray (wavelength365 nm) may be used. From the viewpoints of the cost and the lightexposure energy, a particularly preferable light exposure light sourceis ultraviolet ray, particularly an i-ray.

Further, a curing process of curing a formed pattern by heating and/orlight exposure, if necessary, may be provided. As light or radiationused thereupon, radiation such as i-ray is particularly preferably used.

In production of the color filter according to the first or secondexemplary embodiment of the invention, it is possible to prepare a colorfilter in a desired number of colors, by repeating the image-formingprocess (and as needed curing process) multiple times according to thedesired number of colors in the case of a negative-working color filterand by repeating the image-forming process and the post-baking processmultiple times according to the desired number of colors in the case ofa positive-working color filter.

Examples of the substrates for use include soda-lime glass, Pyrex(registered tradename) glass, and quartz glass used, for example, inliquid-crystal display elements; and those having a transparentconductive film formed thereon, photoelectric converting devicesubstrates, such as silicon substrate, used for example in imagesensors; complimentary metal oxide semiconductors (CMOS); and the like.The substrate may have a black stripe formed thereon for separation ofpixels.

In addition, an undercoat layer may be formed on the substrate asneeded, from the viewpoints of improvement in adhesiveness to the upperlayer, prevention of material diffusion, or planarization of thesubstrate surface.

As the developer used in the method of producing the coloring filter ofthe first or second exemplary embodiment of the invention, any developermay be used as long as it has such a formulation that it dissolves anarea to be removed during development of the colored curable compositionof the first or second exemplary embodiment of the invention (uncuredportion, in the case of a negative-working composition), and, on theother hand, does not dissolve other areas (i.e., a cured portion in thecase of a negative-working composition). Specifically, a combination ofvarious organic solvents, or an alkaline aqueous solution may be used.Examples of the organic solvent include the aforementioned solventswhich are used upon preparation of the composition of the first orsecond exemplary embodiment of the invention.

As the alkaline aqueous solution, an alkaline aqueous solution is usedin which an alkaline compound such as sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium silicate, sodium metasilicate,aqueous ammonium, ethylamine, diethylamine, dimethylethanolamine,tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline,pyrrole, piperidine, or 1,8-biazabicyclo-[5.4.0]-7-undecene at aconcentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.When the developer including such an alkaline aqueous solution is used,generally, the color filter is washed with water after development.

The color filter of the first or second exemplary embodiment of theinvention may be used in a liquid crystal display device or asolid-state imaging device such as CCD, and is particularly suitable fora CCD device or a CMOS device having high resolution exceeding onemillion pixels. The color filter of the first or second exemplaryembodiment of the invention may be used, for example, as a color filterwhich is arranged between a light-receiving portion of each pixel of aCCD, and a microlens that collects light.

EXAMPLES

The present invention will be specifically described below by referringto Examples, but the invention is not limited by them. Unless otherwiseindicated, “part” and “%” are on mass basis.

Examples Relating to First Exemplary Embodiment Synthesis Example A1Synthesis of Exemplified Compound A-3

According to the following Reaction Scheme A1, Exemplified Compound A-3which is a dipyrromethene metal complex compound according to the firstexemplary embodiment of the invention was synthesized.

Synthesis of Intermediate A

To 23.3 g (0.1 mol) of 2-methyl-3-phthaloylpropionic acid, 150 ml oftoluene was added, and the mixture was heated to 80° C. to 90° C. andstirred. To this solution, 17.8 g of thionyl chloride was added bydropping. After completion of the addition, stirring was performed at80° C. to 90° C. for 3 hours to complete the reaction. After completionof the reaction, the reaction solution was subjected to reduced pressureto distill off toluene, thereby obtaining Intermediate A. To thisresidue was added 100 ml of acetonitrile to dissolve it, and theresultant solution was used for synthesis of Intermediate C.

Synthesis of Intermediate C

To 31.4 g (0.09 mol) of Intermediate B synthesized according to themethod described in JP-A No. 10-316654 was added 150 ml of acetonitrile,and the mixture was stirred under heating refluxing. To this solution,an acetonitrile solution of Intermediate A obtained by theaforementioned method was added by dropping. After completion of theaddition, stirring was performed for 5 hours under heating refluxing, tocomplete the reaction. This reaction solution was cooled to roomtemperature, and poured into 1,000 ml of water under stirring, toprecipitate a crystal. This crystal was filtered, washed with water, anddried, thereby obtaining 57.2 g of Intermediate C (yield: 97.3%).

Synthesis of Intermediate D

To 39.5 g (0.07 mol) of Intermediate C obtained by the aforementionedmethod was added 250 ml of 2-propanol, and the mixture was stirred underheating refluxing. To this solution, 5.0 g (0.1 mol) of hydrazinemonohydrate was added by dropping. After completion of the addition,stirring under heating refluxing was performed for 4 hours to completethe reaction. After completion of the reaction, this reaction solutionwas subjected to extraction by adding 500 ml of ethyl acetate and 1,000ml of a 3% aqueous sodium bicarbonate solution. This ethyl acetatesolution was washed with a 3% aqueous sodium bicarbonate solution,followed by drying with anhydrous sodium sulfate. This ethyl acetatesolution was subjected to reduced pressure to distill off ethyl acetate.To the resultant residue was added 300 ml of n-hexane, and the mixturewas stirred to precipitate a crystal. This crystal was filtered, anddried, thereby obtaining 23.9 g of Intermediate D (yield: 78.7%).

Synthesis of Intermediate E

To 59.2 g (0.2 mol) of sodium 3,5-dimethoxycarbonylbenzenesulfonate wereadded 100 ml of acetonitrile and 60 ml of dimethylacetamide, followed bystirring at room temperature. To this solution, 36 ml of phosphorusoxychloride was added by dropping while the temperature of the reactionsolution was adjusted to 40° C. or lower. After completion of theaddition, the reaction solution was heated to 40° C. to 45° C. andstirred for 3 hours, to complete the reaction. This reaction solutionwas cooled to room temperature, and poured into 1,200 ml of ice water toprecipitate a crystal. This crystal was filtered, washed with water, anddried, thereby obtaining 43.5 g of Intermediate E (yield: 74.4%).

Synthesis of Intermediate F

To 21.7 g (0.05 mol) of Intermediate D obtained by the aforementionedmethod was added 65 ml of dimethylacetamide, and the mixture was cooledto 0° C. to 10° C. and stirred. To this solution, 16.8 g (0.0575 mol) ofIntermediate E obtained by the aforementioned method was added bit bybit. After completion of the addition, 8.5 ml of triethylamine was addedby dropping to the reaction solution. The reaction temperature wasretained at 10° C. or lower. After completion of the addition, thereaction solution was stirred at 10° C. or lower for 1 hour, and stirredat room temperature for 2 hours to complete the reaction. This reactionsolution was poured into 1,200 ml of water while stirring, toprecipitate a crystal. This crystal was filtered, washed with water, anddried, thereby obtaining 30.6 g of Intermediate F (yield: 88.7%).

Synthesis of Intermediate G

To 34.5 g (0.05 mol) of Intermediate F obtained by the aforementionedmethod was added 350 ml of methanol, and the mixture was stirred at roomtemperature. To this solution was added 150 ml of a 10% aqueous sodiumhydroxide solution. After completion of the addition, the mixture wasstirred at room temperature for 3 hours to complete the reaction. Aftercompletion of the reaction, 1,000 ml of water was added to this reactionsolution, and the resultant solution was neutralized using an aqueous35% hydrochloric acid solution. The precipitated crystal was filtered,washed with water, and dried, thereby obtaining 28.4 g of Intermediate G(yield: 85.8%).

Synthesis of Intermediate H

To 34.9 g (0.1 mol) of Intermediate B was added 100 ml ofN-methylpyrrolidone, and the mixture was cooled to 5° C. to 10° C. andstirred. To this solution, 14.5 g (0.12 mol) of pivaloyl chloride wasadded by dropping. After completion of the addition, the mixture wasstirred at 5° C. to 10° C. for 2 hours to complete the reaction. Aftercompletion of the reaction, this reaction solution was poured into 1,000ml of water while stirring, to precipitate a crystal. This crystal wasfiltered, washed with water, and dried, thereby obtaining 36.2 g ofIntermediate H (83.7%).

Synthesis of Intermediate I

Dimethylacetamide (30 ml) was cooled to 0° C. to 5° C., followed bystirring. To this solution, 20 g of phosphorus oxychloride was added bydropping. After completion of the addition, the mixture was stirred at0° C. to 5° C. for 1 hour. Then, to this solution, a solution in which36.2 g (0/126 mol) of Intermediate H obtained by the aforementionedmethod had been dissolved in 100 ml of dimethylacetamide was added bydropping. After completion of the addition, 20 ml of phosphorusoxychloride was further added by dropping. After completion of theaddition, the mixture was stirred at 10° or lower for 2 hours tocomplete the reaction. After completion of the reaction, this reactionsolution was poured into 1,500 ml of water under stirring, and then, a10% sodium hydroxide aqueous solution was added to adjust the pH of thesolution to 9 to 10. This solution was stirred at room temperature for 2hours to complete the reaction. After completion of the reaction, thereaction solution was neutralized with an aqueous 35% hydrochloric acidsolution, and subjected to extraction by adding 250 ml of ethyl acetate.This ethyl acetate solution was washed with an aqueous saturated sodiumchloride solution, and dried with anhydrous sodium sulfate. Ethylacetate was distilled off under reduced pressure, and 100 ml ofacetonitrile was added to the residue to precipitate a crystal. Thiscrystal was filtered, and dried, thereby obtaining Intermediate I at28.0% (quantitative).

Synthesis of Intermediate J

To 18.4 g (0.04 mol) of Intermediate I obtained by the aforementionedmethod were added 36.0 ml of acetic anhydride and 13.5 g oftrifluoroacetic acid, and the mixture was cooled to 5° C. to 10° C. andstirred. To this solution, 26.5 g (0.04 mol) of Intermediate G obtainedby the aforementioned method was slowly added in several portions. Aftercompletion of the addition, the reaction solution was adjusted to roomtemperature, and stirred for 2 hours to complete the reaction. Aftercompletion of the reaction, this reaction solution was slowly pouredinto an aqueous solution obtained by adding 1,500 ml of water to 100 gof sodium bicarbonate, while stirring. Then, to this solution were added300 ml of ethyl acetate and 100 ml of acetonitrile, and the mixture wasstirred at room temperature for 2 hours. Then, 35% hydrochloric acid wasadded to this solution for neutralization, and the resultant mixture wassubjected to extraction. This ethyl acetate solution was washed withwater, and dried with anhydrous sodium sulfate. Ethyl acetate wasdistilled off under reduced pressure, and the residue was separated andpurified by silica gel column chromatography (eluent: ethyl acetate).The eluant was concentrated, and to the residue was added 100 ml ofacetonitrile to precipitate a crystal. This crystal was filtered anddried, thereby obtaining 25.8 g of Intermediate J (yield: 58.3%).

Synthesis of Exemplified Compound A-3

To 11.0 g (0.01 mol) obtained by the aforementioned method was added 100ml of methanol, and the mixture was stirred at room temperature. To thissolution was added 2.20 g of zinc acetate dihydrate, and the mixture wasstirred at room temperature for 3 hours. Then, 50 ml of acetonitrile wasslowly added by dropping to the reaction solution to precipitate acrystal. This crystal was filtered, and dried, thereby obtaining 10.2 gof Exemplified Compound A-3 (yield: 87.3%).

An absorption spectrum of Exemplified Compound A-3 in an ethyl acetatesolution was measured. As a result, a maximum adsorption wavelength(λmax) in a visible region was 533.4 nm, and a molar absorptioncoefficient (ε) was 114100.

Synthesis Example A2 Synthesis of Exemplified Compound A-38

According to the following reaction scheme B1, Exemplified Compound A-38was synthesized.

Synthesis of Intermediate K

To 34.8 g (0.1 mol) of Intermediate B was added 150 ml ofN-methylpyrrolidone, and the mixture was cooled to 5° C. to 10° C., andstirred. To this solution, 14.8 g (0.105 mol) of 4-chlorobutanoic acidchloride was added by dropping. After completion of the addition, thetemperature of the solution was returned to room temperature, andstirring was performed for 2 hours to complete the reaction. Aftercompletion of the reaction, the reaction solution was poured into 1,500ml of water while stirring, to precipitate a crystal. This crystal wasfiltered, washed with water, and dried, thereby obtaining 42.4 g ofIntermediate K (yield: 93.6%).

Synthesis of Intermediate L

To 75 g of a zinc powder was added 450 ml of methanol, and the mixturewas cooled to 0° C. to 5° C. and stirred. To this dispersion was added47.5 g (0.162 mol) of Intermediate E. After completion of the addition,36.5 ml of concentrated sulfuric acid was slowly added thereto bydropping. After completion of the addition, the mixture was stirred at10° C. to 15° C. for 1 hour, stirred at room temperature for 1 hour, andthen stirred for 1 hour under heating refluxing. Then, 35 ml ofconcentrated sulfuric acid was slowly added thereto by dropping. Aftercompletion of the addition, stirring under heating refluxing wasperformed for 2 hours to complete the reaction. After completion of thereaction, the reaction solution was cooled to room temperature, andpoured into 1,500 ml of water to precipitate a crystal. This crystal wasfiltered, and washed with water. This crystal was dissolved in 500 ml ofethyl acetate, and the mixture was subjected to filtration to removeinsolubles (i.e., Zn). The resultant ethyl acetate solution wasconcentrated to dryness under reduced pressure, and the residue wascrystallized, thereby obtaining 30.6 g of Intermediate L (yield: 83.5%).

Synthesis of Intermediate M

To 27.2 g (0.06 mol) of Intermediate K and 15.6 g (0.069 mol) ofIntermediate L obtained by the aforementioned methods were added 100 mlof dimethylacetamide, and the mixture was stirred at room temperature.To this solution, 11.0 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) wasadded by dropping. After completion of the addition, the mixture wasstirred at room temperature for 3 hours to complete the reaction. Aftercompletion of the reaction, this reaction solution was poured into 1,000ml of water while stirring, and then, 35% hydrochloric acid was addedthereto to adjust the pH of the solution to 4. The precipitated crystalwas filtered, washed with water, and dried, thereby obtaining 28.3 g ofIntermediate M (yield: 73.4%).

Synthesis of Intermediate N

To 19.3 g (0.03 mol) of Intermediate M obtained by the aforementionedmethod was added 200 ml of methanol, and the mixture was stirred at roomtemperature. To this solution was added an aqueous solution obtained bydissolving 7.2 g of sodium hydroxide in 75 ml of water. After completionof the addition, the mixture was stirred at room temperature for 3 hoursto complete the reaction. After completion of the reaction, 35%hydrochloric acid was added to the reaction solution to adjust the pH ofthe solution to 3. The precipitated crystal was filtered, washed withwater, and dried, thereby obtaining 15.8 g of Intermediate N (yield:85.9%).

Synthesis of Intermediate O

To 18.4 g (0.04 mol) of Intermediate I were added 80.0 ml of aceticanhydride and 15.0 g of trifluoroacetic acid, and the mixture was cooledto 5° C. to 10° C. and stirred. To this solution, 24.6 g (0.04 mol) ofIntermediate N obtained by the aforementioned method was slowly added inseveral portions. After completion of the addition, the reactionsolution was adjusted to room temperature, and stirred for 2 hours tocomplete the reaction. After completion of the reaction, this reactionsolution was slowly poured into an aqueous solution obtained by adding2,000 ml of water to 180 g of sodium dicarbonate, while stirring. Then,to this solution were added 300 ml of ethyl acetate and 100 ml ofacetonitrile, and the mixture was stirred at room temperature for 2hours. Then, to this solution was added 35% hydrochloric acid toneutralize, followed by extraction. This ethyl acetate solution waswashed with water, and dried with anhydrous sodium sulfate. Ethylacetate was distilled off under reduced pressure, and the residue wasseparated and purified by silica gel column chromatography (eluent:ethyl acetate). The eluant was concentrated, and acetonitrile was addedto the residue to precipitate a crystal. This crystal was filtered, anddried, thereby obtaining 22.3 g of Intermediate O (yield: 52.7%).

Synthesis of Exemplified Compound A-38

To 10.6 g (0.01 mol) of Intermediate O obtained by the aforementionedmethod was added 100 ml of methanol, and the mixture was stirred at roomtemperature. To this solution was added 2.2 g of zinc acetate dihydrate,and the mixture was stirred at room temperature for 3 hours. Then, tothis reaction solution, 100 ml of acetonitrile was slowly added bydropping to precipitate a crystal. This crystal was filtered, and dried,thereby obtaining 9.4 g of Exemplified Compound A-38 (yield: 83.9%).

An absorption spectrum of Exemplified Compound A-38 in an ethyl acetatesolution was measured. As a result, a maximum absorption wavelength(λmax) in a visible region was 533.8 nm, and a molar absorptioncoefficient (ε) was 131100.

Synthesis Examples A3 to A18

Molar absorption coefficients of Exemplified Compounds synthesizedaccording to the methods of Synthesis Example A1 and Synthesis ExampleA2 in an ethyl acetate solution were measured using a spectrophotometerUV-2400PC (trade name, manufactured by Shimadzu Corporation). Maximumabsorption wavelengths (λmax) and molar absorption coefficients (ε) areshown in the following Table 1.

Example 1

The following Exemplified Compounds were produced in accordance with theaforementioned Reaction Schemes, and molar absorption coefficientsthereof in an organic solution (organic solvent: ethyl acetate) wererespectively measured using a spectrophotometer UV-2400PC (trade name,manufactured by Shimadzu Corporation). The maximum absorptionwavelengths (λmax) and molar absorption coefficients (ε) are shown inthe following Table 1. In addition, absorbance (Abs) at a measuredmaximum absorption wavelength (λmax) of each colorant was normalized to1.0, and absorption at 450 nm was assessed. Results are shown in Table1.

TABLE 1 Exemplified Compound λmax Abs value at 450 nm when No. (nm) εnormalized with Abs = 1.0 at λmax A-1 532.8 nm 121000 0.010 A-2 533.3 nm118300 0.013 A-3 533.4 nm 114100 0.011 A-7 533.0 nm 117100 0.011 A-21534.2 nm 123000 0.010 A-29 538.7 nm 128300 0.009 A-34 540.2 nm 1079000.012 A-38 533.8 nm 131100 0.011 A-42 546.8 nm 118200 0.007 A-43 540.5nm 105800 0.012 D-1 523.3 nm 82600 0.011 D-2 562.6 nm 82700 0.010 D-6561.4 nm 94200 0.018 D-11 538.3 nm 87000 0.015 G-13 533.5 nm 1195000.008 G-17 533.8 nm 120800 0.009 H-1 532.1 nm 109800 0.008 H-3 532.5 nm113100 0.008 H-11 549.0 nm 132600 0.007 H-12 549.3 nm 128100 0.009 H-13546.3 nm 145700 0.012 H-14 548.5 nm 127400 0.009

The results of Table 1 show that the compounds of the invention havehigh molar absorption coefficients, and low absorbances at 450 nm, andare excellent in color separation, and each are a compound suitable fora color filter.

Example 2 1) Preparation of Resist Solution

The following compounds were mixed and dissolved to prepare a resistsolution.

Propylene glycol monomethyl ether acetate (PGMEA) 5.20 partsCyclohexanone 52.6 parts Binder: (benzyl methacrylate/methacrylicacid/2- 30.5 parts hydroxyethyl methacrylate) copolymer (molar ratio =60:20:20) 41% ethyl lactate solution (EL solution) Dipentaerythritolhexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006part Fluorine-containing surfactant 0.80 part Photopolymerizationinitiator (TAZ-107, trade name, 0.58 part manufactured by Midori KagakuCo. Ltd.)

2) Preparation of Glass Substrate Having Undercoat Layer

A glass substrate (Corning 1737) was ultrasonicated in 0.5% aqueous NaOHsolution, washed with water, dehydrated, and baked at 200° C. for 20minutes.

The resist solution of section 1) was then applied on the clean glasssubstrate to a film thickness of 2.0 μm using a spin coater, and theplate was dried under heat at 220° C. for 1 hour, to prepare a curedfilm (i.e., undercoat layer).

3) Preparation of Colored Resist Solution (Negative-Working ColoredCurable Composition)

Compounds described in the following formulation were mixed and dissolveto prepare a colored curable composition X-1.

Colored Curable Composition X-1

Ethyl lactate 40 parts Methyl isobutyl ketone 40 parts ExemplifiedCompound (A-1) 2.95 parts Polymerizable compound (KARAYAD DPHA 5.89parts manufactured by Nippon Kayaku Co., Ltd.) Photopolymerizationinitiator (CGI-242, manufactured by 1.50 parts Ciba Specialty Chemicals)Surfactant (F-781, manufactured by DIC Corporation) 0.02 part

4) Coating, Light Exposure, and Development of Colored Resist Solution

(Negative-Working Colored Curable Composition)

The colored curable composition X-1 prepared in section 3) was appliedon the undercoat layer of the glass substrate having an undercoat layer,which had been obtained in section 2), using a spin coater so that a drythickness of this coated film became 1.0 μm, to form a photocurablecoated film. Then, heat treatment (pre-baking) was performed for 120seconds using a hot plate at 100° C. to produce colored filters havingany one color from magenta to violet.

Then, using a light exposing apparatus, the coated film was irradiatedwith a light at a wavelength of 365 nm at an exposure amount of 500mJ/cm² through a mask of a line width of 2 mm. After the exposure, usinga 60% CD-2000 developer (manufactured by Fuji Film ElectronicsMaterials), and a 6% CD-2000 developer obtained by diluting 10-fold a60% CD-2000 with water, the film was developed under the conditions of25° C. and 40 seconds, respectively. Thereafter, the film was rinsedwith flowing water for 30 seconds, and spray-dried.

By the above procedure, a pattern suitable for a coloring color filterwas obtained.

5) Evaluation

Storage stability of the colored resist solution prepared above, andspectroscopic properties of the coated film applied on the glasssubstrate using the colored resist solution were evaluated. In addition,developability at use of the 60% CD-2000 developer, and developabilityat use of the 6% developer were evaluated. Evaluation results are shownin Table 2.

Storage Stability

After the colored resist solution was stored at room temperature for onemonth, a precipitation degree of a foreign matter therein was assessedby visual observation according to the following evaluation criteria.

Evaluation Criteria

A: No precipitation was recognized.

B: Slight precipitation was recognized.

C: Precipitation was recognized.

Transmittance Evaluation

A transmission spectrum of the color filter obtained above was measured,and a transmittance at 450 nm was assessed. The larger transmittanceindicates a higher amount of transmission of blue light, and indicatesthat the colorant is excellent as a magenta to violet colorant (i.e., acolorant having any one color from magenta to violet) usable in a bluecolor filter.

Evaluation Criteria

A transmittance at 450 nm when a transmittance at a maximum absorptionwavelength of each colorant was corrected (normalized) to 5% wasdetermined.

A: transmittance at 450 nm≧90%

B: 80%≦transmittance at 450 nm<90%

C: transmittance at 450 nm<80%

Evaluation of Developability

An absorbance at 550 nm of an unexposed area when the 60% CD-2000 wasused as the developer, and an absorbance at 550 nm of an unexposed areawhen the developer diluted to 6% was used were assessed. That is, in thecolor filter using the colored curable composition having gooddevelopability, a colored substance does not remain at an unexposedarea, and alkali developability is excellent; as a result, an absorbanceat 550 nm is reduced.

Evaluation Criteria

A: absorbance at 550 nm<0.01

B: 0.01≦absorbance at 550 nm<0.1

C: 0.1≦absorbance at 550 nm

Examples 3 to 36

Examples 3 to 36 were performed in the same manner as those of Example 2except that Exemplified Compound A-1 used in section 3) “preparation ofcolored resist solution” of Example 2 was replaced with an equivalentmol of Exemplified Compounds shown in the following Table 2,respectively. Results are shown in Table 2.

Comparative Examples 1 to 4

Comparative Examples 1 to 4 were performed in the same manner as thoseof Example 2 except that Exemplified Compound A-1 used in section 3)“preparation of colored resist solution” of Example 2 was replaced withan equivalent mol of the compounds shown in the following Table 2,respectively. Results are shown in Table 2.

Comparative Compound 1

Compound III-1 disclosed in US Patent Application Publication No.2008/0076044 A1

Comparative Compound 2

Compound I-4 disclosed in US Patent Application Publication No.2008/0076044 A1

TABLE 2 Developer concentration Storage dependency Example No. CompoundNo. stability Transmittance 60% CD-2000 6% CD-2000 Remark Example 2 A-1A A A A Invention Example 3 A-2 A A A A Invention Example 4 A-3 A A A AInvention Example 5 A-7 A A A A Invention Example 6 A-20 A A A AInvention Example 7 A-21 A A A A Invention Example 8 A-29 A A A AInvention Example 9 A-34 A A A A Invention Example 10 A-38 A A A AInvention Example 11 A-42 A A A A Invention Example 12 A-43 A A A AInvention Example 13 B-1 A A A A Invention Example 14 B-6 A A A AInvention Example 15 B-8 A A A A Invention Example 16 B-9 B A A AInvention Example 17 C-6 A A A A Invention Example 18 D-1 B A A AInvention Example 19 D-2 A A A A Invention Example 20 D-6 A A A AInvention Example 21 D-11 A A A A Invention Example 22 E-6 B B A AInvention Example 23 E-10 B B A A Invention Example 24 F-2 A A A AInvention Example 25 F-5 B A A A Invention Example 26 F-12 A A A AInvention Example 27 F-13 A A A A Invention Example 28 G-1 A A A AInvention Example 29 G-2 A A A A Invention Example 30 G-11 A B A AInvention Example 31 G-13 A A A A Invention Example 32 G-17 A A A AInvention Example 33 G-18 B B A A Invention Example 34 G-19 B B A AInvention Example 35 H-1 A A A A Invention Example 36 H-3 A A A AInvention Example 37 H-11 A A A A Invention Example 38 H-12 A A A AInvention Example 39 H-13 A B A A Invention Example 40 H-14 B A A AInvention Comparative C. I. Acid C C A B Comparative Example 1 Violet-17Example Comparative C. I. Acid C C A C Comparative Example 2 Violet 49Example Comparative Comparative A A C C Comparative Example 3 compound 1Example Comparative Comparative A A C C Comparative Example 4 compound 2Example

The results of Table 2 show that the colored curable compositionsincluding the coloring agent of the invention have excellent storageproperties in a resist solution, and the coated films formed from thecompositions become a film suitable for a color filter, which isexcellent in spectroscopic property (color separation). In addition, itwas seen that there is no developer concentration dependency, andpattern forming property (developability) is excellent.

Examples 37 to 72 Coating, Light Exposure and Development of ResistSolution (Image Formation)

1) Production of Silicon Wafer Substrate Having Undercoat Layer

A six-inch silicon wafer was heat-treated in an oven at 200° C. for 30minutes. Then, this silicon wafer was coated with the resist solutionprepared in section 1) of Example 2 so that a dry film thickness became1.0 μm. The wafer was dried in an oven at 220° C. for 1 hour to form anundercoat layer, thereby obtaining a silicon wafer substrate having anundercoat layer.

The colored curable compositions of Examples 2 to 37 were each appliedon the undercoat layer of the silicon wafer substrate having anundercoat layer obtained section 1) so that a dry thickness of eachcoated film became 0.8 μm, to form a photocurable coated film. Then,heat treatment (pre-baking) was performed using a hot plate at 100° C.for 120 seconds. Then, using an i-ray stepper light exposing apparatus(FPA-3000i5+, manufactured by Canon), the film was irradiated with lighthaving a wavelength of 365 nm through an island pattern mask having apattern of 1.2 μm² in such a manner that the exposure amount was changedby 100 mJ/cm² within a range of from 100 to 2500 mJ/cm². Thereafter, asilicon wafer substrate on which the irradiated coated film had beenformed was placed on a horizontal rotating table of a spin showerdeveloping machine (DW-30, manufactured by Chemitronics Co., Ltd.), andpaddle development was performed at 23° C. for 60 seconds using 60%CD-2000 (manufactured by Fuji Film Electronics Materials) to form acolored pattern on a silicon wafer substrate.

Formation of Color Filter

The silicon wafer substrate on which the colored pattern had been formedwas fixed on the horizontal rotating table in a vacuum chuck manner,pure water was supplied from an ejection nozzle by showering from abovea rotation center to perform rinse treatment while the silicon wafersubstrate is rotated with a rotating device at a rotation number of 50rpm, and thereafter, this was spray-dried, thereby obtaining a colorfilter.

The formed pattern image having any one color from magenta to violetshowed such a good profile that it had a rectangular cross-section of asquare, which is suitable for an imaging device.

Example 73 1) Preparation of Positive-Working Colored CurableComposition

Ethyl lactate (EL) 30 parts Resin P-1 (described below) 3.0 partsNaphthoquinone diazide compound N-1 (described 1.8 parts below)Crosslinking agent: hexamethoxymethylolated melamine 0.6 part Photo acidgenerator: TAZ-107 (manufactured by 1.2 parts Midori Kagaku Co., Ltd)Fluorine-containing surfactant (F-475, manufactured 0.0005 part by DIC)Colorant: Exemplified Compound A-3 (compound 0.3 part of the invention)

These compounds were mixed and dissolved, to obtain a positive-workingcolored curable composition.

The positive-working colored curable composition thus obtained wasevaluated in the same manner as that of Example 2. As a result, thepositive-working colored curable composition was found to have excellentstorage stability and excellent transmittance.

Resin P-1 and the naphthoquinonediazide compound (N-1) were synthesizedin the following manners.

2) Synthesis of Resin P-1

70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of2-hydroxyethyl methacrylate, and 600 g of 2-methoxypropanol were placedin a three-neck flask which was attached with a stirrer, a refluxcondenser tube, and a thermometer. The mixture was mixed with acatalytic quantity of a polymerization initiator (trade name: V-65, madeby Wako Pure Chemical Industries, Inc.), and was stirred for 10 hours at65° C. in a nitrogen stream. The resin solution obtained was drippedinto 20 L of ion-exchange water with vigorous stirring, and a whitepowder was obtained. The white powder was dried at 40° C. for 24 hoursin a vacuum, and 145 g of Resin P-1 was obtained. The molecular weightwas measured by GPC, which showed the weight average molecular weightMw=28,000, and number average molecular weight Mn=11,000.

3) Synthesis of Naphthoquinone Diazide Compound (N-1)

42.45 g of Trisp-PA (made by Honshu Chemical Co.), 61.80 g ofo-naphthoquinone diazide-5-sulfonylchloride, and 300 ml of acetone wereplaced in a three-neck flask, into which 24.44 g of triethylamine wasadded by dropping at room temperature for 1 hour. After the dripping, itwas stirred for another 2 hours. Then, the reaction solution was pouredinto a large volume of water with stirring. Precipitated naphthoquinonediazide sulfonic acid ester was collected by suction filtration, anddried in a vacuum at 40° C. for 24 hours, to obtain photosensitivecompound N-1.

Examples Relating to Second Exemplary Embodiment

Compounds represented by Formula (A2), Formulae (B2), Formula (C2) andFormula (D2), respectively, may be synthesized by the method describedin US Patent Application Publication No. 2008/0076044 A1.

A method of synthesizing a dipyrromethene metal complex compoundaccording to the second exemplary embodiment of the invention isdescribed in detail by referring to the following Reaction Scheme A2using an example of synthesis of Exemplified Compound A′-3.

Synthesis Example B1 Synthesis of Exemplified Compound A′-3 Synthesis ofIntermediate B′

To 17.4 g (0.05 mol) of Intermediate A′ synthesized according to amethod described in JP-A No. 10-316654 was added 50 ml ofN-methylpyrrolidone (NMP), and the mixture was cooled to 5° C. andstirred. To this solution, 7.62 g (0.06 mol) of 2-chloropropionylchloride was added by dropping. After completion of the addition, thisreaction solution was poured into 800 ml of water while stirring, toprecipitate a crystal. The crystal was filtered, and washed with water.Then, this crystal was dispersed in 250 ml of acetonitrile, and thedispersion was stirred for 2 hours, and subjected to filtration, therebyobtaining 16.5 g of Intermediate B′ (yield: 75.2%).

Synthesis of Intermediate C′

To 13.0 g (0.03 mol) of the intermediate B′ obtained by theaforementioned method and 8.0 g (0.045 mol) of sodium3-mercaptopropanesulfonate was added 50 ml of NMP, and the mixture wasstirred under a nitrogen stream. To this dispersion, 5.5 g (0.036 mol)of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) was added by dropping. Aftercompletion of the addition, the mixture was stirred at room temperaturefor 4 hours to complete the reaction. After completion of the reaction,this reaction solution was poured into 700 ml of an aqueous saturatedsodium chloride solution and 500 ml of ethyl acetate while stirring. Theaqueous sodium chloride solution was removed, and the ethyl acetatesolution was washed with an aqueous saturated sodium chloride solution,followed by drying with anhydrous sodium sulfate. Ethyl acetate wasconcentrated under reduced pressure, and 500 ml of acetonitrile wasadded to the residue to precipitate a crystal. This crystal wasfiltered, and dried, thereby obtaining 16.9 g of Intermediate C′ (yield:97.1%).

Synthesis of Intermediate D′

To 34.9 g (0.1 mol) of Intermediate A′ synthesized according to themethod described in JP-A No. 10-316654 was added 100 ml of NMP, and themixture was cooled to 10° C. and stirred. To this solution, 14.5 g (0.12mol) of pivaloyl chloride was added by dropping. After completion of theaddition, the mixture was stirred at room temperature for 2 hours tocomplete the reaction. This reaction solution was poured into 1,000 mlof water while stirring, to precipitate a crystal. This crystal wasfiltered, washed with water, and dried. To this crystal was added 500 mlof acetonitrile, and the mixture was heated to 50° C., followed bystirring for 1 hour. This dispersion was cooled to room temperature,filtered, and dried, thereby obtaining 36.2 g of Intermediate D′ (yield:83.7%).

Synthesis of Intermediate E′

Dimethylformamide (DMF) (100 ml) was cooled to 5° C., and 19.3 g ofphosphorus oxychloride was added by dropping thereto while stirring.After completion of the addition, the mixture was stirred at 5 C to 10°C. for 1 hour, and a solution obtained by dissolving 36.2 g (0.084 mol)of Intermediate D′ obtained by the aforementioned method in 100 ml ofDMF was added by dropping thereto. After the mixture was stirred at 10°C. to 15° C. for 1 hour, 19.3 g of phosphorus oxychloride was furtheradded by dropping thereto. After completion of the addition, the mixturewas stirred at 10° C. to 15° C. for 2 hours to complete the reaction.After completion of the reaction, this reaction solution was poured into1,000 ml of water while stirring. Then, to this aqueous solution wasadded by dropping an aqueous solution obtained by dissolving 40 g ofsodium hydroxide in 300 ml of water, until the pH of the solution became7. After completion of the addition, the mixture was stirred at roomtemperature for 2 hours to precipitate a crystal, and the crystal wasfiltered, washed with water, and dried, thereby obtaining 40.0 g ofdimethylaminomethylene of Intermediate D′. To 40.0 g of thisdimethylaminomethylene were added 150 ml of ethyl acetate, 30 ml ofmethanol and 200 ml of water, and the mixture was stirred at roomtemperature. To this solution was added 8.5 g of potassium carbonate,and the mixture was heated to 35° C. to 40° C., and stirred for 2 hours.After completion of the reaction, to this reaction solution was added35% hydrochloric acid so that the pH of the solution became from 3 to 4.Then, the ethyl acetate phase was washed with an aqueous saturatedsodium chloride solution, and dried with anhydrous sodium sulfate. Ethylacetate was concentrated to dryness under reduced pressure. To theresidue was added 100 ml of acetonitrile to precipitate a crystal, whichwas filtered, and dried, there by obtaining 36.6 g of Intermediate E(yield: 95.0%).

Synthesis of Intermediate F′

To 4.61 g (0.01 mol) of Intermediate E′ obtained by the aforementionedmethod were added 50 ml of acetic anhydride and 3.5 g of trifluoroaceticacid, and the mixture was cooled to 5° C. to 10° C. and stirred. To thissolution, 5.81 g (0.01 mol) of Intermediate F obtained by theaforementioned method was slowly added in portions. After completion ofthe addition, the mixture was stirred at room temperature for 2 hours tocomplete the reaction. After completion of the reaction, this reactionsolution was slowly added by dropping to an aqueous solution obtained bydissolving 84 g of sodium bicarbonate in 1,000 ml of water. Theprecipitated crystal was filtered, washed with water, and dried. To thiscrystal was added a mixed solvent of 50 ml of acetonitrile and 25 ml ofethyl acetate and dispersed therein at room temperature, and the mixturewas stirred for 2 hours. The resultant crystal was filtered, and dried,thereby obtaining 7.88 g of Intermediate F′ (yield: 77.0%).

λmax in an ethyl acetate solution was 507.1 nm, and a molar absorptioncoefficient (8) was 55600.

Synthesis of Exemplified Compound A′-3

To 1.18 g of zinc acetate dihydrate was added 150 ml of 2-propanol, andthe mixture was stirred at room temperature. To this dispersion wasadded 5.0 g (0.0049 mol) of Intermediate F′ obtained by theaforementioned method. After completion of the addition, the mixture wasstirred at room temperature for 3 hours to complete the reaction. Tothis solution, 100 ml of acetonitrile was slowly added by dropping, andthe mixture was stirred for 4 hours. The resultant crystal was filtered,washed with acetonitrile, and dried, thereby obtaining 4.25 g ofExemplified Compound A′-3 (yield: 81.6%).

λmax of Exemplified Compound A′-3 in an ethyl acetate solution was 535.0nm, and a molar absorption coefficient (ε) was 140800.

Example 1B 1) Preparation of Resist Solution

The following compounds were mixed and dissolved to prepare a resistsolution.

Propylene glycol monomethyl ether acetate (PGMEA) 5.20 partsCyclohexanone 52.6 parts Binder: (benzyl methacrylate/methacrylicacid/2- 30.5 parts hydroxyethyl methacrylate) copolymer (molar ratio =60:20:20) 41% ethyl lactate solution (EL solution) Dipentaerythritolhexaacrylate 10.2 parts Polymerization inhibitor (p-methoxyphenol) 0.006part Fluorine-containing surfactant 0.80 part Photopolymerizationinitiator (TAZ-107, trade name, 0.58 part manufactured by Midori KagakuCo. Ltd.)

2) Preparation of Glass Substrate Having Undercoat Layer

A glass substrate (Corning 1737) was ultrasonicated in 0.5% aqueous NaOHsolution, washed with water, dehydrated, and baked at 200° C. for 20minutes.

The resist solution of section 1) was then applied on the clean glasssubstrate to a film thickness of 2.0 μm using a spin coater, and theplate was dried under heat at 220° C. for 1 hour, to prepare a curedfilm (i.e., undercoat layer).

3) Preparation of Colored Resist Solution (Negative-Working ColoredCurable Composition)

Compounds described in the following formulation were mixed and dissolveto prepare a colored curable composition X′-1.

Colored Curable Composition X′-1

Ethyl lactate 20 parts Methyl isobutyl ketone 60 parts ExemplifiedCompound (A′-1) 4.18 parts Polymerizable compound (KARAYAD DPHA 12.80parts manufactured by Nippon Kayaku Co., Ltd.) Photopolymerizationinitiator (CGI-242, manufactured by 2.00 parts Ciba Specialty Chemicals)Surfactant (F-781, manufactured by DIC Corporation) 0.02 part

4) Coating, Light Exposure, and Development of Colored Resist Solution(Negative-Working Colored Curable Composition)

The colored curable composition X′-1 prepared in section 3) was appliedon the undercoat layer of the glass substrate having an undercoat layer,which had been obtained in section 2), using a spin coater so that a drythickness of this coated film became 1.0 μm, to form a photocurablecoated film. Then, heat treatment (pre-baking) was performed for 120seconds using a hot plate at 100° C. to produce colored filters havingany one color from magenta to violet.

Then, using a light exposing apparatus, the coated film was irradiatedwith a light at a wavelength of 365 nm at an exposure amount of 500mJ/cm² through a mask of a line width of 2 mm. After the exposure, usinga 60% CD-2000 developer (manufactured by Fuji Film ElectronicsMaterials), and a 6% CD-2000 developer obtained by diluting 10-fold a60% CD-2000 with water, the film was developed under the conditions of25° C. and 40 seconds, respectively. Thereafter, the film was rinsedwith flowing water for 30 seconds, and spray-dried.

By the above procedure, a pattern suitable for a coloring color filterwas obtained.

5) Evaluation

Storage stability of the colored resist solution prepared above, andspectroscopic properties of the coated film applied on the glasssubstrate using the colored resist solution were evaluated. In addition,developability at use of the 60% CD-2000 developer, and developabilityat use of the 6% developer were evaluated. Evaluation results are shownin Table 3.

Storage Stability

After the colored resist solution was stored at room temperature for onemonth, a precipitation degree of a foreign matter therein was assessedby visual observation according to the following evaluation criteria.

Evaluation Criteria

A: No precipitation was recognized.

B: Slight precipitation was recognized.

C: Precipitation was recognized.

Transmittance Evaluation

A transmission spectrum of the color filter obtained above was measured,and a transmittance at 450 nm was assessed. The larger transmittanceindicates a higher amount of transmission of blue light, and indicatesthat the colorant is excellent as a magenta to violet colorant usable ina blue color filter.

Evaluation Criteria

A transmittance at 450 nm when a transmittance at a maximum absorptionwavelength of each colorant was corrected (normalized) to 5% wasdetermined.

A: transmittance at 450 nm≧90%

B: 80%≦transmittance at 450 nm<90%

C: transmittance at 450 nm<80%

Evaluation of Developability

An absorbance at 550 nm of an unexposed area when the 60% CD-2000 wasused as the developer, and an absorbance at 550 nm of an unexposed areawhen the developer diluted to 6% was used were assessed. That is, in thecolor filter using the colored curable composition having gooddevelopability, a colored substance does not remain at an unexposedarea, and alkali developability is excellent; as a result, an absorbanceat 550 nm is reduced.

Evaluation Criteria

A: absorbance at 550 nm<0.01

B: 0.01≦absorbance at 550 nm<0.1

C: 0.1≦absorbance at 550 nm

Examples 2B to 41B

Examples 2B to 41B were performed in the same manner as those of Example1B except that Exemplified Compound A′-1 used in section 3) “preparationof colored resist solution” of Example 1B was replaced with anequivalent mol of Exemplified Compounds shown in the following Tables 3and 4, respectively. Results are shown in Tables 3 and 4.

Comparative Examples 1B to 4B

Comparative Examples 1B to 4B were performed in the same manner as thoseof Example 1B except that Exemplified Compound A′-1 used in section 3)“preparation of colored resist solution” of Example 11B was replacedwith an equivalent mol of the compounds shown in the following Table 4,respectively. Results are shown in Table 4.

Comparative Compound A

Exemplified Compound I-3 disclosed in US Patent Application PublicationNo. 2008/0076044 A1

Comparative Compound B

Exemplified Compound III-17 disclosed in US Patent ApplicationPublication No. 2008/0076044 A1

Comparative Compound C

Exemplified Compound III-55 disclosed in US Patent ApplicationPublication No. 2008/0076044 A1

TABLE 3 Developer concentration dependency Compound Storage Trans- 6%CD- 6% Example No. No. stability mittance 2000 CD-2000 Example 1B A′-1 AA A A Example 2B A′-2 A A A A Example 3B A′-3 A A A A Example 4B A′-6 AA A A Example 5B A′-8 A A A A Example 6B A′-11 A A A A Example 7B A′-12A A A A Example 8B A′-14 B A A A Example 9B A′-17 A A A A Example 10BA′-18 B A A A Example 11B A′-20 A A A A Example 12B A′-23 A A A AExample 13B A′-25 A A A A Example 14B A′-30 A A A A Example 15B A′-33 AA A A Example 16B A′-34 B A A A Example 17B A′-35 A A A A Example 18BA′-42 B A A A Example 19B B′-1 A A A A Example 20B B′-2 A A A A

TABLE 4 Developer concentration dependency Compound Storage Trans- 6%CD- 6% Example No. No. stability mittance 2000 CD-2000 Example 21B B′-3A A A A Example 22B B′-7 A A A A Example 23B B′-8 B A A A Example 24BB′-10 A A A A Example 25B B′-12 A A A A Example 26B C′-1 A A A A Example27B C′-2 A A A A Example 28B C′-3 A A A A Example 29B C′-6 B A A AExample 30B C′-10 A A A A Example 31B D′-1 B B A A Example 32B D′-13 B BA A Example 33B E′-1 A A A A Example 34B E′-2 A A A A Example 35B E′-8 BA A A Example 36B E′-9 A A A A Example 37B E′-12 A A A A Example 38BF′-2 A A A A Example 39B F′-11 A A A A Example 40B F′-13 A A A A Example41B F′-14 A A A A Comparative C.I. Acid C C A B Example 1B Violet-17Comparative Comparative B A A C Example 2B compound A ComparativeComparative A A B C Example 3B compound B Comparative Comparative B A BC Example 4B compound C

The results of Table 3 and Table 4 show that the colored curablecompositions including the coloring agent of the invention haveexcellent storage properties in a resist solution, and the coated filmsformed from the compositions become a film suitable for a color filter,which is excellent in spectroscopic property (color separation). Inaddition, it was seen that there is no developer concentrationdependency, and pattern forming property (developability) is excellent.

Examples 42B to 82B Coating, Light Exposure and Development of ResistSolution (Image Formation)

1) Production of Silicon Wafer Substrate Having Undercoat Layer

A six-inch silicon wafer was heat-treated in an oven at 200° C. for 30minutes. Then, this silicon wafer was coated with the resist solutionprepared in section 1) of Example 1B so that a dry film thickness became1.0 μm. The wafer was dried in an oven at 220° C. for 1 hour to form anundercoat layer, thereby obtaining a silicon wafer substrate having anundercoat layer.

The colored curable compositions of Examples 1B to 41B were each appliedon the undercoat layer of the silicon wafer substrate having anundercoat layer obtained section 1) so that a dry thickness of eachcoated film became 0.8 μm, to form a photocurable coated film. Then,heat treatment (pre-baking) was performed using a hot plate at 100° C.for 120 seconds. Then, using an i-ray stepper light exposing apparatus(FPA-3000i5+, manufactured by Canon), the film was irradiated with lighthaving a wavelength of 365 nm through an island pattern mask having apattern of 1.2 μm² in such a manner that the exposure amount was changedby 100 mJ/cm² within a range of from 100 to 2500 mJ/cm². Thereafter, asilicon wafer substrate on which the irradiated coated film had beenformed was placed on a horizontal rotating table of a spin showerdeveloping machine (DW-30, manufactured by Chemitronics Co., Ltd.), andpaddle development was performed at 23° C. for 60 seconds using 60%CD-2000 (manufactured by Fuji Film Electronics Materials) to form acolored pattern on a silicon wafer substrate.

Formation of Color Filter

The silicon wafer substrate on which the colored pattern had been formedwas fixed on the horizontal rotating table in a vacuum chuck manner,pure water was supplied from an ejection nozzle by showering from abovea rotation center to perform rinse treatment while the silicon wafersubstrate is rotated with a rotating device at a rotation number of 50rpm, and thereafter, this was spray-dried, thereby obtaining a colorfilter.

The formed pattern image having any one color from magenta to violetshowed such a good profile that it had a rectangular cross-section of asquare, which is suitable for an imaging device.

Example 83B 1) Preparation of Positive-Working Colored CurableComposition

Ethyl lactate (EL) 30 parts Resin P-1 (described below) 3.0 partsNaphthoquinone diazide compound N-1 (described 1.8 parts below)Crosslinking agent: hexamethoxymethylolated melamine 0.6 part Photo acidgenerator: TAZ-107 (manufactured by 1.2 parts Midori Kagaku Co., Ltd)Fluorine-containing surfactant (F-475, manufactured 0.0005 part by DIC)Colorant: Exemplified Compound A-3 (compound 0.3 part of the invention)

These compounds were mixed and dissolved, to obtain a positive-workingcolored curable composition.

Resin P-1 and the naphthoquinonediazide compound (N-1) were synthesizedin the following manners.

2) Synthesis of Resin P-1

70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of2-hydroxyethyl methacrylate, and 600 g of 2-methoxypropanol were placedin a three-neck flask which was attached with a stirrer, a refluxcondenser tube, and a thermometer. The mixture was mixed with acatalytic quantity of a polymerization initiator (trade name: V-65, madeby Wako Pure Chemical Industries, Inc.), and was stirred for 10 hours at65° C. in a nitrogen stream. The resin solution obtained was drippedinto 20 L of ion-exchange water with vigorous stirring, and a whitepowder was obtained. The white powder was dried at 40° C. for 24 hoursin a vacuum, and 145 g of Resin P-1 was obtained. The molecular weightwas measured by GPC, which showed the weight average molecular weightMw=28,000, and number average molecular weight Mn=11,000.

3) Synthesis of Naphthoquinone Diazide Compound (N-1)

42.45 g of Trisp-PA (made by Honshu Chemical Co.), 61.80 g ofo-naphthoquinone diazide-5-sulfonylchloride, and 300 ml of acetone wereplaced in a three-neck flask, into which 24.44 g of triethylamine wasadded by dropping at room temperature for 1 hour. After the dripping, itwas stirred for another 2 hours. Then, the reaction solution was pouredinto a large volume of water with stirring. Precipitated naphthoquinonediazide sulfonic acid ester was collected by suction filtration, anddried in a vacuum at 40° C. for 24 hours, to obtain photosensitivecompound N-1.

The positive-working colored curable compositions obtained as describedabove were evaluated in the same manner as in Example 1B. As a result,it was found that storage stability and transmittance are excellent.

What is claimed is:
 1. A colored curable composition, comprising: apolymerizable monomer; a radiation-sensitive compound; and at least oneselected from the group consisting of a compound represented by thefollowing Formula (1-A2) and a tautomer thereof and a compoundrepresented by the following Formula (1-B2) and a tautomer thereof:

wherein, in Formula (1-A2) or Formula (1-B2), R₂ to R₅ eachindependently represent a hydrogen atom or a substituent; R₇ representsa hydrogen atom, a halogen atom, an alkyl group, an aryl group, or aheterocyclic group; R₈ and R₉ each independently represent an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an alkoxygroup, an aryloxy group, an amino group, an anilino group or aheterocyclic amino group; at least one of R₂ to R₅, R₈ and R₉ representsa substituent and any one of the substituents represented by R₂ to R₅,R₈ and R₉ is a divalent linking group to bind to -(L)-SO₃ ⁻ or-(L)-SO₃M; M represents a hydrogen atom, or an organic base or metalatom necessary for neutralizing a charge; L represents an alkylenegroup, an aralkylene group, or an arylene group, or a divalent groupwhich may be formed by a combination of divalent groups selected fromthe group consisting of an alkylene group, an aralkylene group, anarylene group, —O—, —S—, —SO₂—, —N(Ra)—, —COO—, —OCO—, —CON(Rb)—,—N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—, —N(Rb)CON(Rc)—, —SO₂N(Rb)—, and—N(Rb)SO₂—, where Ra represents an alkyl group, an alkenyl group, anaryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group,or an arylsulfonyl group and Rb and Rc each independently represent ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, or aheterocyclic group; Ma represents a metal or metal compound which mayform a complex; X₁ represents a group necessary for neutralizing acharge of Ma; X₃ and X₄ each independently represent NR, an oxygen atom,or a sulfur atom, where R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; R and R₈ or R₉ may bindtogether to form a 5-membered, 6-membered, or 7-membered ring; Y₁ and Y₂each independently represent NR or an oxygen atom, where R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group; R₈ and Y₁ may bind together to form a 5-membered,6-membered, or 7-membered ring; and R₉ and Y₂ may bind together to forma 5-membered, 6-membered, or 7-membered ring.
 2. The colored curablecomposition according to claim 1, wherein Ma represents Fe, Zn, Co, V═O,or Cu.
 3. The colored curable composition according to claim 1, whereinMa represents Zn.
 4. A color filter comprising the colored curablecomposition according to claim
 1. 5. A method of producing a colorfilter, comprising: applying the colored curable composition accordingto claim 1 onto a support to form a coated film; exposing the coatedfilm to light through a mask, and developing the coated film to form apattern image.
 6. A colored curable composition, comprising: apolymerizable monomer; a radiation-sensitive compound; and at least oneselected from the group consisting of a compound represented by thefollowing Formula (C2) and a tautomer thereof and a compound representedby the following Formula (D2) and a tautomer thereof:

wherein, in Formula (C2) or Formula (D2), R₂ to R₅ each independentlyrepresent a hydrogen atom or a substituent; R₇ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group, or a heterocyclicgroup; R₁₀ and R₁₁ each independently represent an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an alkoxy group, anaryloxy group, an amino group, an anilino group, or a heterocyclic aminogroup; at least one of R₂ to R₅, R₁₀ and R₁₁ represents a substituentand any one of the substituents represented by R₂ to R₅, R₁₀ and R₁₁ isa divalent linking group that binds to -(L)-SO₃ ⁻ or -(L)-SO₃M; Mrepresents a hydrogen atom, or an organic base or metal atom necessaryfor neutralizing a charge; L represents an alkylene group, an aralkylenegroup, or an arylene group, or a divalent group which may be formed by acombination of divalent groups selected from the group consisting of analkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO₂—,—N(Ra)—, —COO—, —OCO—, —CON(Rb)—, —N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—,—N(Rb)CON(Rc)—, —SO₂N(Rb)—, and —N(Rb)SO₂—, where Ra represents an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group, or an arylsulfonyl group and Rb and Rceach independently represent a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, or a heterocyclic group; and X₁ represents a groupnecessary for neutralizing a charge of Zn.
 7. A colorant, selected fromthe group consisting of a compound represented by the following Formula(1-A2) and a tautomer thereof and a compound represented by thefollowing Formula (1-B2) and a tautomer thereof:

wherein, in Formula (1-A2) or Formula (1-B2), R₂ to R₅ eachindependently represent a hydrogen atom or a substituent; R₇ representsa hydrogen atom, a halogen atom, an alkyl group, an aryl group, or aheterocyclic group; R₈ and R₉ each independently represent an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an alkoxygroup, an aryloxy group, an amino group, an anilino group or aheterocyclic amino group; at least one of R₂ to R₅, R₈ and R₉ representsa substituent and any one of the substituents represented by R₂ to R₅,R₈ and R₉ is a divalent linking group to bind to -(L)-SO₃ ⁻ or-(L)-SO₃M; M represents a hydrogen atom, or an organic base or metalatom necessary for neutralizing a charge; L represents an alkylenegroup, an aralkylene group, or an arylene group, or a divalent groupwhich may be formed by a combination of divalent groups selected fromthe group consisting of an alkylene group, an aralkylene group, anarylene group, —O—, —S—, —SO₂—, —N(Ra)—, —COO—, —OCO—, —CON(Rb)—,—N(Rb)CO—, —N(Rb)COO—, —OOCN(Rb)—, —N(Rb)CON(Rc)—, —SO₂N(Rb)—, and—N(Rb)SO₂—, where Ra represents an alkyl group, an alkenyl group, anaryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group,or an arylsulfonyl group and Rb and Rc each independently represent ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, or aheterocyclic group; Ma represents a metal or metal compound which mayform a complex; X₁ represents a group necessary for neutralizing acharge of Ma; X₃ and X₄ each independently represent NR, an oxygen atom,or a sulfur atom, where R represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group; R and R₈ or R₉ may bindtogether to form a 5-membered, 6-membered, or 7-membered ring; Y₁ and Y₂each independently represent NR or an oxygen atom, where R represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group, or anarylsulfonyl group; R₈ and Y₁ may bind together to form a 5-membered,6-membered, or 7-membered ring; and R₉ and Y₂ may bind together to forma 5-membered, 6-membered, or 7-membered ring.
 8. The colorant accordingto claim 7, wherein Ma represents Fe, Zn, Co, V═O, or Cu.
 9. Thecolorant according to claim 7, wherein Ma represents Zn.